Starting a theme from scratch can be quite daunting.
One of the biggest problems is browser compatibility. What might work in Firefox does not work well in IE6 or 7 for example even for just a basic layout.
The easist way is to use one of Drupal's basic themes such as Bluemarine or Garland or the excellent Zen theme. All the browser compatibility work has been done for the basic layouts. All you have to do is to experiment with the CSS files.
All you do is dowmload it from the Drupal theme site or here http://themegarden.org/drupal50/
Rename the theme's folder and then upload it by FTP to the theme folder in your Drupal installation.
You can then begin to play with the CSS files to amend them theme to what you require.
CSS is beyond the scope of this article.