I've had a brief trawl through the manual (I've no personal experience of Pioneer receivers) but cannot find anything to suggest there is a procedure to "activate" the RCV button.
By way of "most buttons on the remote work" do you mean they all do (other than RCV) or are there others that are suspect?
A simple means of checking whether the ir diode is working is to look at it through a digital camera; press a button and the diode should illuminate with a purplish light. But of course, even if it does illuminate it doesn't necessarily mean to say it's sending the right code, or that the receiver is seeing it correctly.
Perhaps the only alternative is to try a replacement remote. Pioneer have them
here, though
this supplier is slightly cheaper.