Unless I'm mistaken you can't access your "Hotmail" e-mail via Outlook, only via Hotmail.com
The "POP" & "SMTP" settings are used within outlook to set up the e-mail address you will have been provided with by your Internet Service Provider :
e.g. for Ntlworld the POP setting would be pop.ntlworld.com and the SMTP setting would be smtp.ntlworld.com.
Checkign the Home page of any other Internet Service Provider will usually reveal a link to their settings.