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support.microsoft.com/kb/209169 -

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Posted by crouse

(i) From inside outlook Express, click File | Identities | Add New Identity.
(ii) In the New Identity dialog box, shown in type a name for the new identity and, if desired, check Require A password.
(iii) Click OK
(iv) When prompted to switch to the new identity, Click OK. If prompted to keep the active connection to the Internet, Click Yes.
(v) When prompted to set up a new mail account, choose either Create a New Internet Mail Account or Use an Existing Internet Mail Account and input all information
(vi) When prompted to import messages and an Address Book, decide whether or not you want to import. If you choose to import, you’ll be given the choice to import both messages and the Address Book, messages only, Or the Address Book Only.
(vii) Click Next to continue through the wizard to complete the import process.
(viii) To switch back to the original identity, click file | Switch identities.

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Posted by waqasahmad

Step1
Make certain that each person who will have an identity in Outlook Express also has a separate email address.
Step2
Click on the File menu and highlight "Identities." Click "Add New Identity."
Step3
Add the name of your identity and whether you want to require a password. If you don't want anyone else to gain access to your email, you should check the password option and create a password. Just don't forget what the password is.
Step4
Select "OK." The identity window will ask if you want to switch to the new identity. Click "Yes."
Step5
Log on as the new user. You will be asked to provide information about your Internet connection. If you don't know this information, check with your ISP (Internet Service Provider).
Step6
Switch to another identity by clicking on "File" and choosing "Switch Identity." A window pops up with all the identities created in Outlook Express. Click on the name of the mailbox you want to go to, and then click "OK." If the identity is password protected, you must give the password.
Step7
Manage identities by choosing "Identity" on the File menu. Click on "Manage Identities." Understand that each identity has its own messages, contacts and settings.

p:s For more information you can also visit following link:
http://support.microsoft.com/kb/209169

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Posted by sagitraz

(1) From inside outlook Express, click File | Identities | Add New Identity.
(2) In the New Identity dialog box, shown in type a name for the new identity and, if desired, check Require A password.
(3) Click OK
(4) When prompted to switch to the new identity, Click OK. If prompted to keep the active connection to the Internet, Click Yes.
(5) When prompted to set up a new mail account, choose either Create a New Internet Mail Account or Use an Existing Internet Mail Account and input all information
(6) When prompted to import messages and an Address Book, decide whether or not you want to import. If you choose to import, you’ll be given the choice to import both messages and the Address Book, messages only, Or the Address Book Only.
(7) Click Next to continue through the wizard to complete the import process.
(8) To switch back to the original identity, click file | Switch identities.

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Posted by mariuspaul