Sometimes, things end up being so much more simple than thought originally.
Now, before I get flamed for not trying *all* the obvious before posting here;
I thought I did, when I did.. I just never thought to.............
Play Skyrim with Steam-cloud enabled..!!? 
Thing is, all my other achievements had unlocked normally, and were still unlocking, after completion (yet failure to unlock) 'One With The Shadows',
without ever having the cloud enabled. I just let the game sync after exiting, and ran a sync manually a few times when encountering these and similar issues. Earlier I'd posted here that maybe I should patch my copy of TESV to solve this bug, but once I went into the config to arrange that, it turned out the game was set to be kept up to date all the time (so contrary to my beliefs, I was playing the patched version after all). It was only then though, that I encountered the option to use Steam-community overlay during gameplay (again); this was something I'd disabled back in my Call of Duty days as it was causing me to experience major lag and random crashes during coop backthen. Well, so I re-enabled it, went back to my old save and completed the final Thieves Guild quest one more time.
And what do ya know?

Unlocked Achievement 'One With The Shadows'......
...hence, I now have unlocked all 50 of them, got my desired 100% completion,
and therefore need not be frustrated, anymore! Yay.
So remember kids; always (or at least once every year *grins*) keep your Steam-cloud enabled during gameplay.