Answer:
At present Photoshop does not support CSS when rendering a .psd file to HTML.
The only way to use a .psd in web design is to create the image you want displayed (navigation and all) and to then "slice" it in Photoshop. A great tutorial on this is the div tutorial at this site: [http://celestial-star.net]
Once you have created the sliced table of images, CSS can then be hard coded to replace the table, this task though would be a challenge for an expert CSS writer.
you can also import that PSD file into fireworks and slice in in fireworks and export it as CSS and images