Thank you for your response Bucking_Horn.
Couple of things to note, I will fully agree with the assessment that Unbound is the reason that everything keeps going sideways with this basic install. Although I'm a little confused with the "all-in-one multi-software package setup": remark. This wasn't a singular package that was installed with Pi-Hole, PiVPN and Unbound. These were all individual packages that were installed.
As far as your step-by-step approach, if it's just Pi-Hole and PiVPN installed (or even OpenVPN for that matter) the RPi has no problems. But as soon as Unbound gets brought into the mix, things don't continue to work and Pi-Hole doesn't like that. Why else would I be getting the error in debug that Raspbian isn't a supported distro when, as I noted before I even ran the debug, it was saying it was fine. Fun fact, I spent most of yesterday and the day before trying to make this 3 packages play nicely, and as I was going along, I had my Notepad++ open on the other monitor and was trying to go back and forth and I noted about the Distro in step 9 way before I ran debug because I always ran into the exact same issue and was anticipating Pi-Hole to say unsupported distro.
And with PiVPN, it specifically detected Pi-Hole and asked if I wanted to make them play nicely, which as I put in the post, I said yes this time. I have tried to also setup OpenVPN, yes following the Pi-Hole guide, Unbound, following the guide, tried installing in various combinations, admittidly, Unbound being the last, and Pi-Hole always gives me the same error, and for the life of me, I just can't figure it out.
If it would appease the courts, I will happily do an OBS recording, when I get back as I'm leaving for 3 days tomorrow, of the complete process from flash to error instead of putting everything into text. Just for funsies, I'll even have the guides pulled up and to the side so there's no doubt that I am in fact following the guides.
I'm going to assume there's no actual help coming from this thread, so I'm going to just put my backup image back on so my family has my previous Pi-Hole setup while I'm gone... They never realized how spoiled they were with game ads until I decided to try and do things "proper and right" instead of just hacking everything together in a way that things still worked, just in case something happens to me, the old lady said she'll never find someone to figure out just what I did to make things work as I have. So I wanted to do everything by the book, and well, that's not working out for me either. But fear not, if someone wants to tackle issue(s) the actual image of this current setup, I can easily replicate the problem, by following the exact steps I've laid out in my original post, when I get back.