Is Quine-McCluskey the best possible, most optimal way of doing that?
Yes. It is - it's a more machine-palatable way of doing it vs. Karnaugh maps that are mostly targeted for humans.
The problem is generally intractable. The computational complexity is exponential. For a finite automaton that's not a toy example, the computation won't finish in any reasonable time. So while the algorithm is optimal, it's not very useful for realistic problems.
So, the optimal way of doing it is almost irrelevant, since it's entirely impractical: that makes it practically sub-optimal. Yes, it provides optimal results, but the Universe will die before you get them if problems are of a non-trivial size.
There is a reason why Karnaugh maps are done by hand only on small problem sizes: for a problem just a few variables larger, you'd spend a year solving it manually, and even a computer will not finish in a reasonable time with practical problem sizes encountered in programmable logic design, compilers, etc.
So, in practice, you can't use the globally optimal algorithm, and must use approximations that provide locally optimal results: for the same reason that the Travelling Salesman problems of size practical enough the be of real utility can only be solved to yield non-global optima (at least not provably globally optimal).
Both logic simplification and traveling salesman are NP-complete problems, and the only "optimal" ways of solving them that we got are not better, in complexity terms, than an exhaustive enumeration of the solution space.