Win 7 is not XP.
The location for user files is C:\Users in Windows 7.
Documents & Settings is still there for legacy purposes, for systems access only.
Finding the default location for Outlook files is a simple Google lookup:
https://support.office.com/en-us/art...b-0d1892e2aacc
As you have already found, an alternative is to go into Outlook settings and see where it is set to store the PST(s).