Welcome to part two of my series where I explain what classes MLP characters might be if they were in D&D. Once again, bear in mind I am completely inexperienced with D&D, so if anything I say seems inaccurate then feel free to respectfully add your input.
If you haven’t seen the first post I made where I talked about the Mane Six, here’s the link: https://www.fimfiction.net/group/41/crossovers/thread/497225/what-dd-classes-would-mlp-characters-be-pt-1

The Second Party - Starlight & Company

Starlight Glimmer: Sorcerer (Aberrant Mind)

Starlight always seemed more like a naturally-talented, charismatic sorcerer than a studious wizard, so the choice obvious to me. And of course, I had to make her the subclass that specializes with messing with people’s minds.
Her charisma proficiencies would be focused mainly in areas befitting her former status as a cult leader in the show, Persuasion and Intimidation. This makes her an excellent choice to play both the “good cop and bad cop” for the team, highly adept at negotiating with and squeezing info out of hostile or uncooperative characters. Her other charisma-based proficiencies are somewhat lacking in comparison; she only succeeds at deception when she’s able to prepare a lie ahead of time and her performance usually needs a boosting from the next party member.

Trixie: Bard (College of Creation)/Warlock (Fiend-Pact of the Talisman)

Given that performing and entertainment is her trade, I instantly knew that I was going to make Trixie a bard; plus I always found the idea of a stage magician bard to be pretty cool. I initially was going to make her a glamor bard, but I picked college of creation because I could imagine its abilities coming in handy during her magic shows. I personally imagine her instrument of choice (if she has one) would be something like a flute or woodwind instrument.
But I’m sure you’re more curious about why I multiclassed her into warlock. I thought it would be neat if during her party’s adventures, she came across this world’s version of the alicorn amulet. As soon as she tried it on, it put her in contact with an otherworldly being who she makes a pact with to grant her warlock powers. Going solely off the vibes the amulet in the show gave off, a Fiend would be the most likely patron, I think; with the amulet being at the center of this, choosing pact of the talisman was a no brainer, especially when I realized how it could boost her support abilities.
As part of her trade, much of her dexterity is put into sleight of hand. A good chunk of her charisma score is put into performance; while her persuasion and intimidation ranges from okay to abysmal respectively, she does possess high deception. This makes her the best for attracting clients, dazzling them with her performances and making up tall tales about “Trixie’s Great and Powerful Band of Adventurers” to convince them of their qualifications.

Sunburst: Cleric (Arcana Domain)

Let’s be clear, we all know that if the question was “what class would these characters pick if they were playing D&D?”: the answer for Sunburst would always be Wizard. But, I feel it’s even more thematically appropriate for someone like him not having the talent to truly become a Wizard, and instead having to settle for the next best thing.
I initially was going to have it that he started out as a Knowledge Domain Cleric before becoming disillusioned with his faith and switching to Arcana. But I took another look at the Knowledge Domain’s spell list and realized that spells like Command and Suggestion are really going to steal Starlight and Trixie’s thunder. So it’s probably for the best that he doesn’t become a knowledge cleric at all. This way he can somewhat be the utility caster of the group like the Wizard he also wanted to be while also being the expert in many fields of knowledge especially relate anything related to the arcane.

Maud Pie: Artificer (Artillerist/Gunsmith)

I really struggled for a bit to think of a class that can be considered analogous to what does in the show; some would point to that moment where she pummeled a boulder into bits as a sign she would be a barbarian, but she just isn’t the type to rage. For a while I was to just going to make her a fighter and call it at that. But then a more flavorful idea struck me, one that would make her stand out from the rest. I basically decided to turn her into a gunslinger.
Now, I multi-subclassed her into both Artillerist and the homebrewed Gunsmith just to get the point across that she can make both full-sized canons and handguns. Though, reading the Artillerist’s text more closely it may or may not imply that it can already make guns, or at least a rough approximation of a gun.
I imagine the backstory reason for why she became an Artillerist was to protect her village, which is subject to a lot of encroachment from bandits and hostile neighboring countries because of how rich in minerals it is. She probably joins the party after they somehow help provide a permanent solution to keep her home safe, allowing her the chance to travel the world like she always wanted.

This party turned out to be far more caster-oriented than I initially expected, but I think this helps give them a different flavor from the other parties I’ve come up with. I see this as more of a band of mercenaries than a classic heroic band of adventurers. This is the type of party that will always look for the easiest way to get their jobs done above all else, even if it means doing some morally questionable actions.

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some would point to that moment where she pummeled a boulder into bits as a sign she would be a barbarian, but she just isn’t the type to rage.

I disagree. If we consider the way Pinkie talks about Maud, she's actually very emotional. It's just that she doesn't show outward signs.

If we consider that, I would say barbarian suits her quite well. You just can't tell she's raging until you suddenly find yourself tied into a pretzel. Tell me you can't imagine her going all Ivan Drago, saying, "I must break you."

As for Sunburst, I could see him being an Order of Scribes wizard.

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Nah man. Starlight would be an Arcanist, Sunburst would be an Invoker and Maud would be a berserker

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Maybe. But I still feel that giving her proficiency with firearms gives her something unique among the rest of the cast while matching theme that this party invokes. I also like how suitably impersonal and cold-blooded firearms are compared to melee weapons, very fitting for someone who’s rage isn’t expressed very openly. If we’re talking about a strength-based class that could suit, might I suggest the Pugilist homebrew as an alternative?

As for Sunburst, yes he would want to be a Wizard. He certainly has a personality befitting the Order of Scribes. But I’d like to imagine that much like in the show, he is sorely lacking in terms of actual talent needed to be actually be one. He knows almost every spell recorded in available texts and understands perfectly what each spell is capable of. But when it comes time to actually cast the spell, he falls short every time with the exception of some cantrips. In other words, in a magic school he is someone that aces the written tests but fails the actual performance tests. That’s why I decided to make him someone who has to borrow power from a god in order to be able attain abilities even remotely comparable to a Wizard. Actually, under different circumstances, if he hadn’t discovered the Arcana Domain faith he might’ve made a pact with an otherworldly being and become a Warlock instead.

This actually reminded, I’ve figured since my first post what subclasses Twilight would be and I’d be interested to hear your thoughts. How does Order of Scribes Wizard/Phoenix Sorcerer sound?

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May I ask why?

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Okay, how about Sunburst having two levels in wizard with a book with pretty much every spell, cantrip-9th level? That would make sense, as he knows the spells, but lacks the ability to use most of them.

This actually reminded, I’ve figured since my first post what subclasses Twilight would be and I’d be interested to hear your thoughts. How does Order of Scribes Wizard/Phoenix Sorcerer sound?

Clockwork soul, one hundred percent. It not only fills her orderly and structured personality, but also her role as a Barer of Harmony. Phoenix would have been my choice before Tasha's, though.

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Oh, also, with Trixie, I would say College of Glamour/ Illusion wizard. College of Glamour is all about being the center of attention, and she's really pretty good with illusion spells.

Also, also, maybe Maud would be a living weapon (forged heart) monk?

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I like the idea that her sorcery magic is less controllable than her Wizard magic, adds more flavor. That’s why I chose Phoenix. I got the idea after remembering her fiery form from Feeling Pinkie Keen.

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Starlight experiments with spells, which is what Arcanists do. They aren't bound by magic schools and experiment with magical effects. sunburst isn't very good at magic, but he knows a lot about it. Invokers gain their powers through great study and a more direct line of power from their god. Which fits with Sunburst having been a student at Celestia's school. As for Maud being a berseker, she has incredible strength and an amazing connection to the rocks, which is part of a berserkers kit.

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Alright but just bear in mind that I’m sticking mostly to 5e classes for this, so don’t be surprised if I don’t choose classes like that in the future. Also, drawing power from a god sounds an awful lot like a cleric.

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It's not. Clerics have to go through rites to do what they do. Invokers have a direct connection to their god, sometimes even having a piece of that god in them. And honestly, I'd recommend going with 4e classes instead. Way more variety.

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I originally did have her as a Glamor Bard and Pinkie as a Creation Bard as you suggested. But it’s when I realized how useful those creation abilities would be for stage magic that I decided to swap them, and I figured the change wasn’t too unbelievable. As you said before, the creation subclass still puts a lot emphasis on performance. Also, I already have an illusionist planned for a later post, though you do make a good point.
Also, for Maud I once again suggest Pugilist as an alternative for a multiclass focused on hand to hand combat. I already have two other monks planned.

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I imagine that Twilight, though mechanically a multiclass wizard/sorcerer, would be treated as if she was a single class. Kind of like how in Harry Potter, one is born with magic, but if they want to actually use it they have to study. Also, if Celestia is a goddess in this, divine soul might work, too.

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You could make Trixie a glamour bard/alchemist artificer and reflavor the potions as fireworks. I just really feel glamour bard fits her best as, like I said, it isn't just performance, it's being the center of attention. Creation really fits Pinkie's randomness and how she's always pulling things out of her mane or random places.

As for Maud, I'm actually playing a 'gunk' in one campaign. He's a living weapon, were touched monk/lycanthrope (Grimhollow's Guide) that uses guns. You said you would like to give her something unique, maybe something like that? Maybe not the lycan part, though it would be cool if that was just her 'emotional side' coming out to the surface. Other than that, maybe a monk/artificer?

Monk just makes a lot of sense for her, especially the living weapon monk, and doubly so the forged heart option. The forged heart's unarmed attacks are considered adimantine, meaning it auto-crits objects, like boulders, and the first hit can do an extra 2d6 for 1 ki. That's on top of the extra damage all living weapons get at 6th.

I know you might not like using homebrew, but this was made by one of the guys that worked on Ebberon, so it's borderline canon.

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With Trixie, I’m still attached to the idea of her multiclassing into warlock later on, especially since for a while I wasn’t able to find any other characters who I could imagine as warlocks until recently. I think we can both agree that implementing the alicorn amulet at some point during her adventures would be a smart way to make that happen; write so that putting it on the amulet puts her in contact with an otherworldly being that she then makes a bargain with.

By the way, I’m pretty alright with using homebrew if it makes sense. That’s why I suggested giving Maud the Pugilist homebrew for her to multiclass into.

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The amulet coming into play would certainly be interesting, but if you're looking to mirror canon, I wouldn't make it a permanent part of her kit. Otherwise, it could always just be a powerful enchanted item. Maybe it's a sentient item with warlock levels. That would be interesting. Then Trixie would be free to focus on just being Trixie.

I'm not familiar with the pugilist. D&D Beyond has a couple dozen pugilists.

Also, what about the Student six? Gallus and Smolder would definitely be rogues. Gallus would probably be a swashbuckler and Smolder an arcane trickster (because dragon=magic). Yona would be a totem barbarian. Silverstream would be a tempest domain cleric. Ocellus would be a moon druid. Sandbar... honestly, kinda like the idea of him just being a dude. No class, no level, just a guy with really, really good luck so nothing actually hurts him.

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Not mirror canon perfectly. Just in ways that would make for interesting story and character development. Like I said already, this version of an amulet acts as her means of directly contacting her patron, and by those means she gains her warlock abilities. The amulet also has the effects of the Pact of the Talisman, which would boost her support abilities as a bard.

The Pugilist Class I’m referring to is the one by Benjamin Huffman. Link Here: https://www.docdroid.net/ttVzNfE/benjamin-huffman-pugilist-class-pdf#page=6
This is apparently one of the most popular homebrews for 5e, so I highly recommend checking it out. It’s subclasses seem well thought out.

As for the Student Six, we’ll get to them soon enough

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Looking back at some of these, I noticed this;

I wasn’t able to find any other characters who I could imagine as warlocks until recently

and I have to simple say; Tempest Shadow. You're welcome.