I own both a Vive and PSVR, love them both.
Vive is amazing for the overall quality/fidelity of experience, flexible steam platform, and all the great PC only type experiences like Dolphin VR were you can play Wind Waker or Metroid Prime in VR (AMAZING!).
But if you're looking for a cheaper point of entry PSVR really punches above it's weight when you compare it to the Vive and the expensive ass PC I had to build to play it.
I have loved my experiences with both so far and can't wait to see the tech mature. Only jump in gaming I can compare VR to was going from 2d to 3d (like snes mario to mario 64). As a kid from the 80's I remember just sitting there staring at Mario 64 in my local Blockbuster in awe. VR has been like that for me. In particular RE7 is god damned amazing in VR. It's like experiencing some kind of lucid nightmare. And it's so much better in VR. Try playing it on a flat screen after playing it through in VR and it sucked in comparison.
If you have a playstation and haven't picked up a PSVR I highly recommend it. And then go buy Thumper, Superhot, Skyrim, RE7, Moss, Astrobot, Doom, Farpoint, and Firewall.