I'm trying to put together SharePoint 2007 (and, eventually, 2010) training materials for experienced ASP.Net developers, and having done SharePoint for years, I don't really remember where the worst sticking points were at the beginning - not to mention the amount of Googlable SharePoint content is greater by an order of magnitude than two years ago.
That said, what SharePoint concepts are the hardest to grasp, and/or what parts of SharePoint are esoteric enough to be non-obvious to a newbie SharePoint developer just diving in?