Outlook 2002/20023 and Outlook 2000/98 in Corporate/Workgroup mode allow you to have as many profiles as you want. Generally, we recommend one profile per computer user (creating a Windows user account for each user is best, especially if you use Windows XP, but more hassle if you use Windows 98/ME). If you use Outlook for personal and business email, you'll probably want two profiles.
If you need to add a second account to your current profile, go to the Tools, Services menu in Outlook then click the Add button and choose the Internet Service. You can then start with this step.
Use the following steps to create a new profile using Outlook 2000 Corporate mode. See Outlook 2002/2003 instructions for the specific screens used in those versions. Instructions for Outlook 2000 Internet Mail Only (IMO) mode are here.
Note that Outlook 2000 Corporate/Workgroup supports only POP3 and Exchange accounts.

Close Outlook.If you use the Category
view in Windows XP's Control Panel, look for the Mail applet in the User
Accounts category.

Select
the option to use the following information servicesIf you use an Exchange account, your administrator will tell you how
to set your account up or set it up for you.
Tip: Use a descriptive name, so you know what the profile contains without looking at it's Properties.
Select the authentication method your email provider uses. If you aren't sure which one to choose, check with your provider.
After configuring the account, you'll be given the opportunity to select the personal folders you wan t to use. If you are moving to a new computer or have a personal folder store (*.pst) you want to use, click the Browse button and find it. Otherwise, click Next.
The final screen displays the accounts you have in your profile.
Click Finish.