As for the Enclave being evil, it's easy enough if you take into account what bad things Eden (on the radio) has to say about the Brotherhood of Steel. James knew that the Brotherhood tried to help Project Purity so he'd know Eden was lying about the Brotherhood (I liked that in Fallout 1 the Brotherhood wasn't popular and was considered as a threat, something that Fallout 3 played down and simplified quite a bit by making the Outcast faction). To anyone with half a brain (doesn't include Nathan in Megaton) it would be clear that the Enclave has an agenda and that the propaganda is meant to alienate the Brotherhood from the population of the Capital Wasteland. That is the opposite of what Three Dog is trying to achieve and it's obvious that Three Dog and James had a chat about the Enclave so James would know what to expect from them when they reached the Jefferson Memorial.
I can't see James as Enclave material. IMHO Project Purity is much too noble and selfless for a reformed Enclave scientist.