The plan is to have powerups that unlock new regions, yes. The difficulty is in coding in the "locks". I have no confidence in my ability to procedurally generate maps that you can't get stuck in (by accidentally bypassing a lock and then not being able to navigate the area beyond it), so the player will have to be equipped with a teleport device to return to a safe haven.
Basically, there are the following major aspects that need to be done:
* Make it interesting. Nobody wants to explore a boring map. This means making lots of scenery, making varied terrain, having the right number of enemies, having enjoyable music, all that jazz.
* Make it have meaning. If there's no purpose behind exploration, the player loses interest fast. They need to have a reason to go hunt down that powerup. In your standard Metroidvania, these reasons mostly take the form of locked areas, and to a somewhat lesser extent simple curiosity. This means figuring out what the powerups do and then coding up locking systems, which will probably need to be different for each powerup type, and of course will need to be adaptable to varied local terrain.
* Make it playable. Tighten up the controls so the player can easily perform the actions they want. Make combat enjoyable. Make platforming challenging without being a chore. Make obtaining powerups rewarding, and ensure the player always knows where to go next without having to hold their hand.
Up to now I've been focusing on the first point, making a map that looks like a map and not just a collection of tunnels. I'm still a long ways away from finishing that aspect, but it may be time to start considering the other aspects as well.
For what it's worth, "Plop down some rooms and then make corridors between them" is one of the dominant map generation algorithms in NetHack, a famously long-lived and popular roguelike game.