Hey Dave,
I'm a newbie to the web development world as well. I've been working with HTML and CSS for about 2 years now, and have just picked up PHP thanks to Larry's book. I wouldn't have a clue how to use Adobe Dreamweaver as I don't really like the idea of WYSIWYG editors for HTML.
I would recommend learning HTML 4 first before moving onto HTML 5. I'm still trying to wrap my head around HTML 5 and CSS3.I will be sticking with CSS2 and HTML 4 until I find a better resource for learning the new technologies. I'm purely explaining how I have learnt HTML and CSS, I'm not a professional. There are some cool resources which I found (unfortunately) after I had completed learning the HTML and CSS essentials:
HTML Dog - Follow through the HTML and CSS tutorials
CSS Tricks - Great articles on some of the cool tricks available
Smashing Magazine - More web development in general than actual coding
Also, instead of Adobe Dreamweaver give Notepad++ or Sublime Text (tad more advanced) a shot. When I started out I set myself a goal and stuck to it. That goal was to never use a WYSIWYG editor until I knew what I'm doing. I still use a text editor as I like the feeling of control and freedom. Work hard on following a standard such as HTML 4 Transitional or HTML 4 Strict so you can get the hang of writing correct markup. If you get stuck on creating something, search it in google and read some example markup. Don't just copy it into your project though, understand it. You may have to pull individual tags out of that markup and search them to see what they mean. I used this technique to give me a deeper understanding into how the different elements interact and how different developers come to their solutions.
Designing for IE 6 and IE 7 is always fun...
~Sam