I'll get to work on the topic for an RPG Maker community thread, but my impressions after a few hours:
As been said, if you know RPG Maker VX Ace, you do already know a lot about this program. The lay-out is very similar, the icons look different and such, but if you're used to VX Ace, it's really easy to ease into it. It's basically VX Ace, but built on-top of.
So what's different? I'll go in order of what I noticed, and not what is important.
-The obvious comes that the default tilesize and screen resolution are bigger. 48x48 pixels, as opposed to 32x32, and 816x624 as opposed to 544x416 default.
-BUT, it's really easy to make whatever resolution. A lot easier than I expected, actually. You can change the tile-size to anything really, and the resolution to anything. So you could make 1080 x 1080 tiles, or 4k resolutions, if you really wanted too.
-Mouse and touch controls are well-implemented and a nice feature.
-Games now launch with a built-in options menu by default, easy enough to edit it and easy to make keyboard/gamepad configs on the options menu.
-Plugins are nicer than expected. Outside of Javascript being overall easier and more well-known, can now super easily turn plug-ins on and off with in-engine commands.
-Tiling is a LOT better now, by default you have multiple layers so you can take sprites and easily layer them over another, which is nice and makes mapping a lot easier now. You can layer the B, C, E, D, E, etc. tiles now, even from tiles from themselves. Can also easily make however many layers you like.
-You can now edit the game while you're testing it, which is nice.
-Games now by default unpack all the RTP assets into your game folder, but you can remove what you're not using as it doesn't require the whole RTP anymore, just what you're using.
-Audio has some cool new effects and can now easily save your position in music and stop it and then resume it. Sound effects can now play over each other infinitely instead of canceling each other for a new sound effect, and the fading seems better to me.
-Some 'event triggers' are MUCH better than they once were. For example, if you had an event chase you, it used to be very finicky with detection in VX Ace, but it's much smoother and simpler now. Also a lot easier now to get events to be able to walk on-top of other events, something that was more challenging to do in VX Ace by far.
-Tile triggers are now on the tilesheets, unseen numbered tiles to layer on other tiles that secretly trigger things.
There's other small things, and still adjusting to a few things, but what I've noticed so far. There's niceties and some things are easier than ever, and some new features seem like they will be very helpful in the long run, but it also definitely feels like VX Ace expanded and improved in areas than completely new. The biggest draw remains to be the multi-platform support the higher/customizable resolution and tile-size, as well as plugins being much easier to use and better implemented than scripting in VX Ace.