I made the move from Camera Raw to Lightroom a couple of years ago. The basics of how to process files are still the same. The database aspect turns out to be more useful than I expected, and it fit in well with the way I was already organizing my assignments. The biggest thing for me was being able to save pre-sets for everything in Lightroom, including Export presets (rather than fiddling with the dialog box in Camera Raw every time). Presets really speed up my workflow.
Edit: oh, yeah, suggestions on how to learn. I started with a very small set of photos (a few folders) and started playing with the import settings, making presets, etc., before starting to use it every day. I don't recall using any specific book, and I hate watching tutorial videos.