I think you are at least asking the right question here, which implies that you actually understand the matter better than you think you do.
When you try to make a one-to-one pairing between two sets, there are any number of ways you could choose to match them up. Comparing two finite sets, you will get the same result no matter how you pair up the elements: One of the sets in particular will be smaller and the other bigger, or else they will be the same size.
When you try this with infinite sets, funny things happen. Consider pairing up the set of all positive integers with the set of all positive even integers. There are several ways you could do this, with several different results. You can easily find a pairing scheme that shows the sets to be equal in size. You can also easily find a pairing that shows the set of all integers to have many left-overs (infinitely many in fact), showing that this set is the larger. What to make of this?
Cantor made this definition (perhaps arbitrarily): If you can find ANY WAY to pair up the sets to make them come out equal in size, then the sets are equal in size.
But if you find a way to show one set is larger (that is, has left-overs) and you CAN’T find a way to pair them up one-to-one, then the set with the left-overs is the larger set. Now we run into a problem – the very problem that you are hinting at:
If you CAN’T find a one-to-one pairing scheme, does that mean it can’t be done? OR does it simply mean you aren’t clever enough to find the scheme, or that you haven’t tried hard enough?
Thus, to show that one set is larger, you actually have to PROVE that there CAN’T be any one-to-one pairing scheme, no matter how clever you are.
Cantor’s diagonal argument does this. Notice that he doesn’t actually show any particular alleged one-to-one scheme and then disprove it. Rather, he shows a generalized idea of a one-to-one scheme, that could actually be any scheme, and then proves that it can’t work. Thus, what the diagonal argument proves is that ANY scheme you could possibly come up with is susceptible to that change-the-digits trick, and thus that ANY scheme would leave you with left-over numbers in the real-number column.
Thus, the diagonal proof shows that the reals will out-number (or should I say, “out-infinite”) the rationals no matter how you try to pair them up. This is the sort of thing you must do to show that one infinite set is larger than some other infinite set.