When someone asks me how they can build a web site I usually say, “It’s kind of a long process.” I don’t know that I’ve ever finished a web site. I’m always tweaking, looking for a better way to present the content. I always recommend learning to use HTML and css rather than going straight to a program like Dreamweaver. I’m still learning to use these properly.
htmldog.com is a nicely done site that has beginner, intermediate and advanced guides on HTML and CSS.
Start with the CSS Beginner’s Guide and the HTML Beginner’s Guide.