As far as using dreamweaver you might want to start by downloading one of the CSS templates from
www.csstemplates.org Open the template up in Dreamweaver and that will help you get a feel for how the program works.
Once you become familiar with the functions you can always Google different things if you need help. That's how I learned a lot about the program. I also bought Dreamweaver for Dummies and that helped a lot!