Well, here it is. This is why I will never own a Mac or iPhone. Apple makes everything more difficult due to poor design and then tries to pass it off as a security feature. Just trying to complete the phone call was a fiasco. My original appointment was canceled somehow so I had to reschedule... twice.
After multiple attempts to connect with the representative via phone, we tried a couple other options with iTunes. No luck. Then, for some reason, she had me go to the AppleTV website and sign-in there. I've never been to that site before nor have I ever had an interest in AppleTV but I was able to sign-in to my account there. It looked different but my iTunes account information was there. She had me delete my credit card info, sign-out, sign back in and re-enter the credit card. Then we went back to the iTunes app on my PC, signed-in and attempted to purchase the same song again. It worked. Problem solved.
Why my iTunes account would be connected to an AppleTV profile that I never created, why that connection wouldn't be perfectly synced or that one could affect the other is beyond reason, but that's Apple for you. So desperate to be cutting edge that they forget the basics of simply making sure that their product is functional and reliable. They'll never accept that pretty isn't practical and sacrificing dependability just to make it unique is what keeps Microsoft and Android customers loyal.
Anyway, five-stars to Apple support for effort. That's one thing I can say for Apple, they have the best tech support hands-down. They certainly need it.
Now, I have to figure out how to unlock my wife's account since Apple is not accepting the answers to her security questions and not allowing her to reset them. Apple support is already telling us that this being the case, they can't help and we're screwed. The account, purchased content and any money on it is lost.