Just know that I love Vayne spotting. It's my favorite past time.
IMO, Jinx is better just because she's a more consistent ADC. She can bully a lane with a hard support and generally gets snowballing a lot easier. I think Vayne is an amazing pick in comps where you're versing 1-2 solid front liners and you just really need to destroy one of them in quick succession. She's also better against comps without a ton of point and click CC. When a Vayne can be clicked on and destroyed, it just makes you want to drink bleach. She's a great split pusher simply because, if you're good enough, it's almost impossible to 1v1 a Vayne. In other words, Vayne is really, really good at destroying a single target at a time. Once you pile 2-3 people on top of her, she just pops like a zit.
Jinx is an amazing ADC in arguably more team comps and situations. Jinx with
,
and
will just roflstomp any tanky team comp and blow up front lines hilariously fast. On top of the fact that Pow Pow disintegrates objectives like they're made of wet tissue paper on fire. Her laning phase is safer with a root and slow for self peel as well as Fishbone's harass range make her a pretty harsh lane bully.
As far as the LCS goes, Vayne is likely better simply because Vayne with a coordinated team is just retarded. Jinx is my go-to comfort ADC for soloqueue, though, because she doesn't need to rely on the rest of her team quite as much.
Both are God-tier ADC's and I think if you want to play a champ who just explodes single targets like an assassin, you can't really go wrong with Vayne.