VR is very fun, but just be aware that motion sickness and VR legs are definitely a real thing you should be aware of. You'll more than likely get used to it overtime, so don't let that put you off, but just be aware that RE7 especially can be kinda rough on VR if you're just starting out. It's absolutely fantastic, but it might make you a little queasy lol. Astrobot on the other hand is a great starting point, and as crazy as it sounds, WipEout is comfortable to play as well (surprisingly for a game that has you hurtling around tracks at like 300mph).
I'd also avoid Skyrim as a beginner game, because even though it's super cool, like I can't believe I was impressed by the opening cart ride which I think everyone has seen like 100 times before, it's kinda similar in terms of RE7 when it comes to locomotion, so it can make you feel a bit weird when you're starting out.
A good thing to keep in mind, or what's helped me at least, is that if you're playing a game with movement, and not just like a light gun thing, a cockpit of some description helps. Flying around on Zone of the Enders 2 (another great one to try) is way more comfortable than just walking forward on Skyrim, for example.
Also, if you do pick one up, keep in mind that there are plenty of demos on the PSN store to try out, including some almost demo disc-esque things, with multiple demos in one.