Have you bought CS4? Dreamweaver CS4 has some great new features.
If you're unfamiliar with HTML/CSS, I would highly recommend Head First HTML & XHTML with CSS.
For free tutorials I would agree that a good place to start is Adobe. There is a list of available tutorials
here.
Lynda.com has a wide range of video tutorials for $25 per month or alternatively
Safari online books has over 6500 books and videos including 9 specifically on Dreamweaver CS4.
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Denise - Your Organisers