Unless you're willing to learn CSS, the WordPress loop and a little PHP, you will have some trouble "getting" the theming in WordPress.
I suggest starting here: How To Create a WordPress Theme: The Ultimate WordPress Theme Tutorial
and then there are extensive docs on WordPress Theme Development too.
That's what I'm trying to do. I have my CSS sheet set up for my site, and I can make a WordPress theme that looks like my site.
What I really want to do is theme WordPress while keeping my Dreamweaver template intact (at least to some extent). That way, if I decide I want to tweak my site, I don't have to reskin WordPress all over again. I want it to just update the way Dreamweaver updates templates.
P.S. I don't know if it makes a difference, but I'm using CS5
Personally I'd just do the entire site in WordPress. You'll be able to edit the page content just as you would a "post", and once you get the hang of the WordPress theme modifying that HTML is a snap.
Here's a handy cheat-sheet to help unravel some of the mystery behind the WordPress php code in your theme: