I couldn't agree more with @egray. Coding from scratch is the only way you can truly have full control over how everything looks and feels down to the very pixel, not to mention there are no limitations or restrictions on what you can do. Not to mention you don't need any proprietary software like Dreamweaver.
My suggestion is to build a personal website as your sandbox. Make a good design mockup and try to get it into css/xhtml. You will learn all about good markup along the way as you figure out how to make it work. This is how I got into it and now that I'm on my 5th design iteration for my site I can finally say I've mastered css/xhtml. It took me about 2 years to get really good.
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