I'll confirm this as well. I'd initially ordered two Collector's Editions just to be safe. Once I found out that I only needed one on each account, I used the second one for my wife's account. Our set up is as follows:

Me
  • PC - Standard Digital Download
  • PS3 - Collector's Edition (physical copy)

Wife
  • PC - Collector's Edition (physical copy)

Both accounts have the CE bonus items but only I can play on either system.

As a side note to this, you will get the 30 days of free time for both copies of the game that you register to your account if you go the route I went. Once the PS4 version is released, I expect to also see those 30 days applied to my account.