Respectfully disregard much of denisb1's post. Sync Services were disabled by MS in the SP1 Update issued about the time Lion came out as Apple stopped supporting their iSync sync conduit, and MS went pretty much Exchange only for calendaring and contact management.
The "trick" to adding contacts is to drag-and-drop a contact's .vcf file or a group of contacts .vcf file (that will read something like "Some Guy and 19 others" - but keep these "grouped", read on).
Put your .vcf file where you can get at it, then open Outlook. Click on the .vcf file and drag it to the Category in the Category Pane you want to coordinate your relevant contacts to - and your People Section will populate with those contacts and tag them with the Category you dragged them to (Manager, Friends, Family, etc.). You can then tag them with additional categories or change the categories as you see fit.
Keep in mind that these People (contacts) will remain local only, and won't sync anywhere else, unless you've got an Exchange account to sync them to. Outlook 2011 worked this way as well after SP1 came out.