Hi emodied,
I did an online search and found this to be a common issue with lot of users. Many of them were able to get this fixed just my uninstalling and re-installing People app. Its worth giving a shot. Please see People app for Windows: FAQ for more information: http://dell.to/174Didb
Good Luck.
Thanks and Regards,
Appu S
I have 2 different facebook accounts, when I click "Add an account" in People App for the first time, it connected to my first facebook account. Then I remove this one by going to the online setting, and completely remove this account. Now I want to add my second facebook account but everytime I choose connect to facebook, this app automatically connect to the old one?

Chowhound
Comic Vine
GameFAQs
GameSpot
Giant Bomb
TechRepublic