I spent part of my day fighting with CSS for an email template. CSS support is poor in both desktop and web clients, and much worse than in current browsers.
Gmail, for example, does not support in either the head or the body of HTML email. You have to explicitly set style attributes on individual nodes. You might as well be using tags!
You can’t assume that images will be downloaded, so the mail has to make sense without them. And forget iframes.
CampaignMonitor seems to have the definitive guide to CSS support.