Configuring Windows Live Hotmail follows the same general sequence as configuring most any mail client for most any mail server — mail servers are more or less the same everywhere, though the services and ports can vary. Put another way, you need to acquire some information for the target mail service (the server host names for the mail-send and mail-receive paths, whether IMAP or POP3 is used, whether SSL/TLS is used or not, and possibly the TCP portI(s) involved (if not the standard ports, and this is rare), and these configuration details are covered in the Apple cheat sheet (below).
Here are what I think the Hotmail settings are (I don't have a login over there, so I can't confirm these):
Windows Live Hotmail appears to use the the pop3.live.com server and TCP port 995 (that's POP via TLS/SSL) as the receive path with your Hotmail email address as your user and your Hotmail password, and the smtp.live.com server and TCP port 587 (That's SMTP submission port with TLS/SSL, again with your Hotmail email address and password as your credentials).
Configure these settings manually (or possibly via the Wizard) and you should be good to go.
Microsoft Windows Live Hotmail does apparently also permit outbound SMTP connections via port 25, but I'd recommend against configuring and using that port, as that port tends to be blocked outbound from many networks.