So, I've played both modes. The biggest difference, outside of the obvious skill set, is the plot. You're not doing the exact same plot beats as both Marisa and Reimu, which is a good thing. They fight bosses in different orders (and certain bosses are just missing), for different reasons and have several different side quests that they can do. I would strongly suggest you play them both, but please do turn on turbo mode, because it makes the game faster and more fun.
Who to play first? Honestly, it doesn't matter. Some say Reimu is easier, but honestly, I found Marisa to be stronger for most of the game, only kinda falling behind Reimu in end game where she can take a bit longer to bring down certain bosses. The main difference is, Marisa has no homing attacks, so you have to be slightly better at timing and aiming. But if you're only going to play one... do it as Marisa. She's just more fun.
This game is a step up in nearly every way from the prior game, Scarlet Curiosity. The art is much nicer, the graphics are a massive leap in most areas and the maps are even better. You now have the ability to run, which speeds up exploration and what little backtracking there is. While you have fewer skills, they can now level, Ys 7 style, to a maximum of 10, making them stronger, giving better range, etc.
Skills now have their own cool down, rather than a universal pool of energy to draw from. Since skills feel like they're stronger in this game, especially Reimu's, which several of them home in, I can see that this was an attempt at balancing, to remove the ability to just spam the strongest skills. At the same time, given how you can enhance your skill regen rate to make it, at most, a few seconds, it's kind of moot. Perhaps in a challenge run...
What is better, though, is the platforming. While still not amazing, jumping feels much better, and the real topper is that there's fewer chances to just fall off if you overshoot things. Plus, you now seem to not lose any money if you do fall into a pit and have to respawn, so a massive frustration has been lifted. Especially because there's now even more stuff to spend your hard won currency on.
... I say this, and then I got to near end game, where the platforming really becomes terrible. But it's still actually better than anything Scarlet Curiosity threw at you, since none of it is over money sucking pits.
The mechanics from the previous game when it comes to equipment is back in full force. Randomly generated stats for every item you find, can buy from Nitori and the gacha machine (because of course). But new to this is the ability to reforge gear via Kogasa. Every item has a range where the stats can fall (some equipment simply cannot give certain stats)... but again, it's also random. You cannot pick and choose what stats are altered, meaning that you could get an excellent piece of kit, have Kogasa work it and it turns out to be way worse. You can pay more to keep rerolling stats, but like the gacha machine, it's pure RNG gambling.
I believe the main purpose of Kogasa is to find a piece of gear that has great ranges (so basically end game stuff) and just pay her to reroll it, in essence just giving yourself constant rerolls, rather than pray to the RNG to get another of that item to play the stat RNG game. But it's still lacking in a lot of aspects, and is honestly still terrible.
Oh, and like the prior game, both characters share largely the same armor and accessories, only the weapons are really different. Such a let down.
New to this game, however, is the ability to guard. While not super vital for much of the game, it's still pretty good; if you can pull off a perfect guard, you get a countdown where time slows globally, save for yourself and your skill timers, to go full ham on every enemy around you. The downside is, of course, only certain attacks can be guarded, depicted with a blue glow. The length of your guard can be changed via equipment stats, so it's just another thing that gets piled onto the RNG of gear. However, you do not get the slowdown if you manage to guard a spellcard, despite it having the blue glow. And even then, you'll only get a reduction in damage, not a total negate.
Guarding does, however, become vital with one certain boss near the end, and in the post game challenges. You'll know 'em when you get to 'em. And curse them.
You can also, now, just heal if you want in battle. It has its own cool down, and it completely removes any and all healing you could find in stages or as enemy drops. You can have a maximum of 4, and they recharge one after the other, not all at once. It's not ideal, but it makes surviving some battles possible, unless you are a 1cc grazing god.
The game has side quests, little things here and there that you can do to get currency, random items and, most importantly, stones that can be used in Nitori's shop to strengthen your stats. The cost increases with each level, of course, but you can increase everything, from how much HP you have to how long your perfect guard lasts, even increasing your base item drop rate. By the end of the game, and with every side quest done, you will have them all maxed out... but that doesn't do much, since the game is over at that point. You should wisely pick and choose, rather than just go down the list.
The game reuses a lot of assets from the prior game, so be ready to hear the same tracks, find yourself in many of the same areas and, of course, fight most of the same bosses. While there is new stuff here and there, it's more sparse than it could be. Most enemy patterns are different, however, especially the bosses. But so many of them love to spam this one tornado attack...
If you're a fan of ARPGs, this is pretty good. If you're a fan of 2hu, this is obvious. If you enjoyed the prior game, then you'll feel mostly at home here.