Found this which has a bit of blurb on hotmail and the AOL settings:
http://www.emailaddressmanager.com/t...-settings.html
On my version of Outlook I go into Tools then accounts and then select the mail account I want to edit and paste in the smtp outgoing mail address.
For hotmail try setting the outgoing mail to the
mx1.hotmail.com although it might not work as from I seem to remember hotmail doesn't work on smtp or pop3 but is a web based service so might not play ball for Outlook.