I generally go from a photoshop file to dreamweaver and hand-code it. The way Id go about it is to use a CSS style sheet to set the back ground (thats the basic layout) and have the navigation taken out of the image.

Id then add a navigation div and use the images/text as separate files to create the navigation

and then finally add another div to make the main content box

that probably sounds extremely complex, but the best way to get a hang of it is by going to other peoples websites and view all of their source and work out what is doing what etc.