Of course, as a sibling comment notes, unlabeled graphs are often more interesting, for which one has to look at equivalence classes of adjacency matrices. The spectrum is nice here because it is automatically invariant to vertex permutations and hence a graph isomorphism invariant. The existence of nonisomorphic cospectral graphs is not immediately obvious, although there are simple examples, and that there are infinite families of cospectral pairs is even less obvious. So at the very least, it's interesting that the spectrum is not a complete invariant, and that it does work well for certain classes of graphs.
It doesn't relate to machine learning (which is what I assume you mean).
Yes the concrete expression of the isomorphism would be as a mapping between the labels.
Given that the paper linked to is by Brendan McKay et al, it seems reasonable to mention that nAUTy works by finding (efficiently) all permutations of the labellings that result in an automorphism of the graph.
But, speaking of information, consider this: the adjacency matrix of a simple, loopless graph of order n is a symmetric n x n matrix with all zeroes on the diagonal. That means the adjacency matrix contains (literally) n^2/2 - n bits of information, while the number of connected graphs of order n as n -> infinity grows exponentially [0]. That implies that for the purpose of telling two graphs of the same order apart, the spectrum is of fairly limited utility, which is what I was thinking of when I wrote that it was not an interesting invariant.
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[0]: https://users.cecs.anu.edu.au/~bdm/papers/BCM_Connected1.pdf