Thanks for the reply Raze! I'll go through your suggestion in point for to keep it simple for us both
Firewalls/AV Programs: I only use the Windows (Win7) Firewall, and no other antivirus at all. Basically because everytime I tried one, it seriously messed my PC.
I aksed my friend, and she hasn't changed or manual updated either on her comp either. I will ask if there was an auto update in that time period.
Other programs, network related stuff: Yes, definitely closing everything today when we tried getting it to work again. As an aside, I HAD lots of things open some of the other times we played, and things worked perfectly.
Hosting: Tried that too. When I hosted, it took almost 5 mins for hers to load. Note, thats due to this Unknown Error, NOT a crappy PC. When things were working, I'd invite her, the game would prompt me that she joined, then within about 15-30 secs, she'd be in. Now, it gets to about 80% in the load bar..sits for about 2 mins, the loading bar goes away, and the only thing moving is the little spinny icon.
When she hosted and I joined, it was basically the same thing, just slightly faster (still over 4 mins to get in) on my end.
Ways to Connect: We were using the in game invite thing, then the steam lobby (all prior occasions). Today we tried direct connect as well as a VPN program called Evolve, which another forum post said worked for them with D:OS. Nothing was any improvement.
Verifying: Have both done that. Yet to try afterwards though. No mods of any kind are running.
Winsock Resetting: This seems to be the only option now. We will try that this morning.