If your Hotmail account works with Entourage, the incoming and outgoing mail server information is available via your Hotmail account preferences in Entourage which you can easily check.
In order to access a Hotmail account with the Mail.app requires installing a 3rd party httpmail plugin for the Mail.app which adds the httpmail protocol to Mail and the account type to choose from when creating the account in Mail.
The httpmail plugin can be installed here.
http://www.versiontracker.com/dyn/moreinfo/macosx/18189
Since you want to get away from MS software, why not make a clean break by switching to and using a different free email account provider?
Gmail is free and Yahoo may be free outside of the U.S.
If not, you can get a Yahoo Mail Plus or paid account for only $19.95 (U.S.) per year.