Step 1:
Find some type of inspiration; an illustration, another website, a movie. Pick some colors you like, and just go to town in Photoshop.
Step 2:
Write out all your HTML, keep it valid, keep it POSH. Create all pages, paragraphs, etc.
Step 3: Polish your design into a nice layout. Copy some text from the HTML page you have started to get a good color scheme going, pick the right type faces, letter spacings, ect.
Step 4: Take your design and try to make your HTML site look like it using CSS and a few images (the less images the better, for loading reasons).
Actually I wrote an article you might find interesting
things-to-think-about-before-creating-a-website