Either find a template online you can open inside of Dreamweaver and start playing around with it. Or you can look for some online tutorials. If you just Google "Dreamweaver Tutorials" there are tons.
I learned by just poking around and trying things. I did buy a book from Barnes and Noble to help me discover things I probably wouldn't have learned on my own and it was helpful.
You really have to just find out what works for you.
Also if you go to the "File" / "New" menu Dreamweaver has some basic CSS templates you can start with. You can choose between 2 or 3 column. That's also a good way to start.
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Don't put the cart before the horse. Plan your website, thencreate it.
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