Small Business Server has Exchange, SQL Server, and a few other options depending on the version, and Active Directory. AD creates a 'domain' that users and other servers can join. When they join, they are given rights, and you can control their access to files and services, and allow other servers to trust certain users without a lot of intervention on your part. Exchange is basically a central database of email that can be backed up live, and has other benefits, like the calendaring mentioned above.
I use SME for customers to filter viruses and spam for their Exchange servers, since windows based software to do that is very expensive and doesnt always work that well. I dont need an AD domain for my own office, so I use SME as my email server. Both SBS and SME are great at what they do, and they have a few similar features, but they are very different.
Windows Server is very stable. Windows really shines at basic file and print sharing, and it runs easily on any hardware you can think of just because there are drivers for everything. But I would never attach a Windows server directly to the web, so I dont use Windows servers as gateways or firewalls. I install one nic in them and hide them behind a firewall.
SME really shines at webserving, virus & spam scanning, firewall, email, (with pop3, imap, and horde) and you can serve files, although I'm not conviced that samba is as good as windows with heavily used database files like MS Access. But do you really want to store your files on your firewall in any case?
SBS, and the software to do backups, etc. is very expensive, while SME is priced right. But if you need SBS, cost isnt really an issue...