Excluding the more advanced features of TFS, I don't think it's a product that needs specific Getting Started advice considering your prior experience with source control systems - the discoverability of the tools in VS is good (visually indistinctive icons in VS2012 notwithstanding...) so please experiment - you can always Undo
I think the most important thing to remember is that the Solution Explorer view does not map 1:1 with source-control, because you can have files in the Solution that aren't in TFS, and contrarywise: files in TFS that aren't in the solution.
I don't have any experience with SourceSafe (besides reading data-loss and corruption horror stories) so I can't provide any specific examples, but I picked up TFS very quickly when I started playing with it in 2007.
Come to think about it, the only issues I had with TFS as a newcomer was understanding the sometimes cryptic error messages when working with project binding (VS > File > Source Control > Change Source Control), which unfortunately is something you will encounter if you're importing an existing project into TFS - creating a new project from scratch is considerably simpler.
I also recommend putting the Source Control Explorer button on your main toolbar, it's a very useful tool and window and I don't know why the VS guys chose to bury it under a View submenu.