There are three introductory webcasts about
- Signing up for Office Live Small Business
- Working with e-mail
- Getting started with a web site
on Microsoft's UK Small Business web site. They show the UK version of Office Live Small Business, but they're equally useful for all US Office Live Small Business versions as well - the interface is the same. The videos are short - 3 to 5 minutes each - but a quick and good overview if you're just starting out.