Additionally, is the 'Internet Browser' for PlayStation 4 fully updated?
Yes

Are both the PlayStation 4 and Windows device fully updated with the current version?
Yes. It is not a windows operation system though, my laptop is a MAC and they're both up to date.

Again, I have no issues with other characters or the game itself, it's just my main character that is locked out without a VPN for some reason...

Is Internet Explorer/Microsoft Edge fully updated for Windows?
-
Have you attempted to power cycle the router(s)/modem(s)? (Unplugging the device and leaving it idle for 10-15 minutes)
Yes multiple times

Are there any others on the network when playing Final Fantasy XIV?
I live with many others so there are always someone using the network.