I'm going to give an answer that discusses some things that the other answers don't go into as much detail on. In particular let me try to explain why the results you mention on classical groups having the same $n$-level correlations are in fact relevant to the number theory situation. It will build off KConrad's answer in some ways.
The Katz-Sarnak book proves theorems about zeroes of $L$-functions in function field setting. These are defined by exact analogues of the definitions of $L$-functions, over another field. Of course, as KConrad points out, these aren't the same as $L$-functions over a number field, and many of the families considered in the Katz-Sarnak book don't match the families of interest over number fields. But some match, and this has been rectified in later work.
One key advantage of the function field setting is that the situation is conceptually clearer. The $L$-function is a polynomial, and by the Grothendieck-Lefschetz trace formula it is the characteristic polynomial of some naturally defined matrix (the action of a Frobenius element on a Tate module or etale cohomology group). So we have no difficulty interpreting the zeroes as eigenvalues of a matrix. Moreover, this matrix lies in some matrix group, the monodromy group of the family.
These matrices are over an $\ell$-adic field and so can't naturally be viewed as unitary matrices. But Deligne (with Weil first in some cases) showed that if we base change to the complex numbers, they are conjugate to unitary matrices. So in fact the zeroes of the $L$-function are eigenvalues of elements of the maximal compact subgroup of some algebraic matrix group. So in this setting, the question of why we should expect the zeroes to behave like eigenvalues of random unitary matrices is not mysterious at all - it's the simplest possible behavior they could have, given that they are eigenvalues of unitary matrices.
In fact Deligne did more and showed that these Frobenius conjugacy classes are equidistributed in the maximal compact subgroup of the monodromy group. In other words, the statistics of any continuous function of the set of zeroes at all matches the statistics for random matrices in some compact group. Such a powerful result doesn't come without a cost, and it has two. First, we may not know what the group is. Second, this statistical equivalence only shows up in the limit as we take the finite field size to infinity. In this limit, the number of zeroes is fixed, so we can take the same compact group each time. However, in the number field settings, people always consider limits where some parameter controlling the number of zeroes grows.
The first cost was dealt with by Katz-Sarnak by computing the group in some important cases. They found that, while a priori it could be any group at all, in fact it was usually a classical group (which is something Katz had already noticed in some of his earlier investigations). So they focused attention on the maximal compact subgroups of classical groups.
The second was and is more difficult to deal with. However, since the transfer from the function field case to the number field case is conjectural anyways, one merely has to guess how to transfer statistics from finitely many zeroes to infinitely many zeroes, and then perform the calculations to do the transfer. They guessed that taking the limit of distribution of the smallest $k$ eigenvalues in a family of matrices in larger and larger groups would match the distribution of the smallest $k$ zeroes in $L$-functions over number fields. The first few chapters of the Katz-Sarnak book are then devoted to calculating these limits, which is the part that looks like honest random matrix theory.
So Katz and Sarnak combined algebraic geometry - the results of Deligne and the monodromy group calculations - with random matrix theory - these calculations in the limit as the size of the classical group grows - to obtain precise predictions for the statistics of zeroes of $L$-functions over number fields. These predictions have then been expanded and refined in later work.
I guess this is all a bit removed from your motivating question, which is how that random matrix theory can help in number theory. Unfortunately I don't know how much cutting edge research in random matrix theory is really needed, because we know of no rigorous relationship between $L$-functions over number fields and any kind of random matrix, so thus far random matrix theory has mostly been used to give predictions, and the predictions we already have are hard enough to try to prove that any property of random matrices found by more powerful techniques might be even further out of reach over number fields. However, on a positive note, I would suggest you check out Terry Tao's latest blog post, which is on a question involving random matrices, still unsolved, motivated by number theory (in fact, possibly motivated by a joke I made in a talk?).
