I suspect that it's not vsync, but in fact reprojection. If you miss frames SteamVR halves the frame rate and "fills in" every other frame with a faked one to attempt some semblance of smooth play. Turn off reprojection in the SteamVR settings (performance section) to see what your true frame-rate is - it'll probably be closer to 80 I reckon.
I totally don't recommend leaving reprojection off though - you'll start feeling really sick. Instead just use it to see how far off 90 you are, mess with AA and SS, and then turn it back on.