I think it's an "other things being equal" issue, whereby mostly the other things are not equal.
OTBE, more hours make for a better pilot, more experience, better judgement, better capability etc. etc.
There is much more to it that that, however. Just a few examples:
A very experienced pilot lays off for a long time through illness or whatever, comes back to flying, and is as accurate etc. as if still current. Another is so rusty it is like a rough early solo pilot.
There is some evidence that people can think themselves through an experience and subsequently perform much better for real than someone who has not mentally rehearsed it. In both cases there are no "hours" doing it beforehand, but one is better than the other.
So, in general, people vary so widely from one to another that it is difficult to generalise meaningfully.
But if you knew nothing more about two pilots than one having a lot more hours than another, with which would you prefer a loved one to have their first flight with?