Dreamweaver CS 5.5 - the missing manual by David Sawyer McFarland is one book that tries to not only introduce dreamewaever but also the concepts of web design. Something of a nice blend between conceptual learning and quick reference has made the book worth every penny one spend on it. As it is said "Jack of all trades, Master of nothing" the book finds difficulty to concentrate specifically to a group of people, whether novices,beginners,experts or dreamweaver regulars, but caters to everyone. The contents are quite insightfully segmented so that seasoned users can skip quite first few chapters and take off from where you are comfortable with.
Tutorials provided are well refined and nothing of sort of redundancy in contents occurs anywhere. The book will help one to get a real picture of dreamweaver's capabilities. Well structured formatting of book makes it a quick and complete reference while the layout, flow of language and various side notes,tips and illustrative examples makes it a good and engaging read. Coming to advanced sections such as templates,dynamic sites and libraries the author does a wonderful job in explaining the conceptual and usage aspect of those features.
Bottomline: go and grab one of those copies, start working with dreamweaver and when you are stuck just go for the read.