Divinity: OS is probably more immediately inviting to the newer CRPG player, particularly the combat. Its turn-based combat is widely hailed but the storyline and general writing have received a mixed reception.
If you want something more story-heavy, I'd recommend Pillars of Eternity.
I'd say that Divinity's combat is easier to understand, but PoE is the easier game once you grasp the core combat concepts (excluding Path of the Damned maybe, but if you're new that probably isn't an option anyway). Also, Divinity does a ton less hand-holding in terms of progression and presents way more opportunities for you to fuck yourself over by doing things out of order or in ways that weren't intended/'canonical'.
PoE's quest structure is actually generally very simple. It's rare to get a quest where you aren't told almost exactly where to go or nearly all of what you need to do. In Divinity, on the other hand, you can end up spending several hours on a puzzle, or worse, you can end up not knowing what to do or where to go and end up missing 1-2 levels worth of content, causing you to push into content that's far too hard for you. If you do ever figure out how to get back to the old content afterwards, you're overleveled and the plot is broken. The game has tons of freedom, but that freedom has costs, and it definitely isn't something that I would recommend for someone new to the genre. I think the minor challenge of coming to grips with PoE's combat system is more suited for genre newcomers than dropping them into the chaos cauldron that is D:OS.
