Hotmail accounts work well with Outlook Express (as might be expected because of its associations with Microsoft). The following link tells you how to configure OE5 to access your hotmail account. http://www.netmag.co.uk/ie5/oe-hotmail.htm
You can use it for any POP3 mail services. You just need to know 1) Your username 2) Your password 3) The POP3 address (eg pop.freeserve.net) and 4) The SMTP address (eg smtp.freeserve.net). The website usually gives all this email info which you plug in when you run the new account wizard in OE.