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Install wordpress.
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Get the style.css file from the default theme (at /wp-content/themes/twentyten/style.css).
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Open that file, you will see it is very well structured and commented. With just a few copy/paste from your current site’s css to this file you will start to see the changes.
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If after playing with the CSS you feel the need to change some html elements, start with the index.php file under the twentyten folder. That will change your homepage among other pages. When you have that done, you could need to do similar modifications to page.php, archive.php and single.php. Also, header.php holds the top part of the html body, of course shared by all the pages, same as footer.php and sidebar.php.
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When you are done, change the name of the theme: you need to change the folder name (twentyten > mytheme) and the first lines on style.css (Theme Name). You should probably leave the Author part in its place of course. If you skip this step your customizations could be lost with the next upgrade of your wordpress install if done via wp-admin. Once done you will need to activate your customized template in wp-admin.
