HTML is the basics of web design and programming; you cant get any simpler and is the best place to start.
Dreamweaver is just an editing program which helps you see both the code and deisgn view. Not everyone uses the program as it comes down to personal preference; some prefer something simple like Notepad.
Best place to start is HTML and CSS, then work your way onto other things.
I found
http://www.htmlgoodies.com a great place to learn when I self-taught.