So I made one aborted attempt at playing BG2 a number of years ago and couldn't get into it.
Having played Divinity and PoE do you guys think the game might be a bit more accessible now? How does it compare to PoE overall in terms of difficulty and understanding the systems in place?
It sort of depends which parts of BG2 threw you for a loop. If it was just the general flow of a D&D-like ruleset, in terms of the way that attacks are resolved (and the overall frequency with which things actually land), the ideas of saving throws, or the general pace of Infinite Engine style RTwP combat, then playing Pillars will have probably done a pretty good job of preparing you for it.
If it were the actual specific minutiae of 2e AD&D, and how to build and play within that ruleset in a way that's effective, then you'll probably be just as lost as you ever were. For the most part, nothing is going to help make it easier to learn how 2e works, because 2e was always a completely shitty ruleset and its only saving grace was that the sheer volume of content it supported made it extraordinarily flexible.
That said, a lot of people really love it, and although I'm definitely not one of them, if you have a copy of the game available to you and you feel like you could give it another shot, it's probably worth trying to play it just in case it does click for you the way it did with so many other people.