Your first pic shows a cap of 144 and sync on, which means it wouldn’t render any frames above 144. Which means any performance that would hit above that target is lowered. to that cap, which in turn impacts on your average FPS (but prevents screen tearing).
Your second pic has it (effectively) off (as you have set to unlimited FPS at the point where it should stop) and has higher average FPS and higher lowest 5% margins.
This depends greatly on what you are wanting for each game and what performance you can hit. There isn’t a “best” setting. Gsync and Vsync on will prevent tearing but will add input latency. Gsync on but vsync off (where you are hitting above your monitors refresh rate) won’t have any added input latency (and can minimally decrease it) but then you risk screen tearing.
Triple buffer Vsync adds even more input latency (though it should be fairly minimal). Perhaps turning this down to a single frame would help your issue? It may not but I would say this is worth a shot.
As long as you have it set to do this, yes it will
(barring any stupid bugs).
Are you using a SSD or a Hard drive? My friend with a 3090 and similar performance issues to you has a Samsung 970 evo plus and has these issues so I don’t think drive speed is an issue here but figure it is worth asking, and if you both have the same SSD and same GPU there may be an issue here.