Interesting, I hadn't realized that Microsoft released a Windows Live email client. Anyways, SMTP stands for Simple Mail Transfer Protocol, think of it like HTTP (Hyper Text Transfer Protocol) but for email instead of webpages. Well what you need to do is go to the preferences (don't exactly know where that is) and find the section where you type in the SMTP. Now assuming your email ends with @live.com, you'll want to type in:
smtp.live.com
port 587 (or 25)
TLS (or SSL)
Into the corresponding boxes (shouldn't be too hard to figure out), and anywhere where it asks for a username and/or password, you type in your full email address and your password.
Good luck.
