I had same problem as you just now, also using VorpX with Oculus Rift CV1 (and Mass Effect 1 from Steam). I noticed that when I start Mass Effect 1, I get the “allow this program to make changes to your computer?” Windows popup dialog. When you say “Yes” to that, I believe Windows then runs that program (in this case, Mass Effect 1) under a different user profile than the one you are logged in as. I theorized that this might prevent VorpX from being able to see that the MassEffect.exe program has started, because it only scans programs started by the same user who started up VorpX.
So I exited VorpX and restarted VorpX using [right-click]->[Run as administrator] on my VorpX desktop icon. Then I started Mass Effect 1, got the “allow this program to make changes to your computer?” popup as usual, clicked “Yes”, Mass Effect 1 continued starting up, and VorpX hooked immediately.