Dreamweaver is the best web design program you can get your hands on, no question about it. If you are just starting off, I'd highly suggest you look for web templates you like and consider purchasing one. Sites like http://www.dreamtemplate.com
are excellent places to grab an up to date, professionally coded, website for a relatively cheap price - and at the very least you might find something there that inspires you to design your own site around. If you expect people to take your website seriously, it will need a modern look - don't just start from scratch and create something that screams 1990's - most web users know within a few seconds whether or not they trust the site they are on and what information is has to offer or sell.
Regardless of what program you choose, having a basic understanding of HTML and CSS is important. But Dreamweaver is the best program you can use for web development. If you want to get up to speed on CSS, HTML, or any other Adobe product, I'd suggest the tutorials at Lynda.com. There is a subscription fee, but short of reading countless books (boring) or going back to college (expensive), Lynda.com is the best site for learning a new PC skill. We use it where I work and it's been an invaluable tool for me.