Follow The Steps Below to Create a new account from Control Panel:
- To create a new account
- Click Start–> Click Control Panel–> Then Click on User Accounts.
- Click Create a New Account in the User Accounts window.
•A User Accounts window appears. Enter the name of the new account and click Next.
•The next window asks you to pick an account type. Choose Computer Administrator or Limited by clicking the appropriate radio button.
•If you’re not sure, click each one and read the list of actions that can be performed by the account type.
•When finished, click the Create Account button.
•The new account now appears in the User Account window.
winxpexpert 
If you have to create a lot of user accounts command prompt is the easiest way
How to create new users from command prompt?
Go thru this link to know to create User account thru command prompt.http://www.microsoft.com/resources/documentation/windows/xp/all/proddocs/en-us/net_user.mspx?mfr=true
net user /add (Add user)net user /Delete (Delete User)You can execute these two commands to add/ delete users from command prompt