Is there a theoretical maximum useful keysize given the block-size?
If you are asking about a truly theoretical limit for a theoretical block cipher (as opposed to a practically usable one, like AES), you could calculate the number of possible keys like this:

A block cipher, together with a key $k$ ($|k|$ = $M$), describes one of many possible random permutations: For every plaintext block, there is exactly one ciphertext block. The number of possible blocks is simply $2^M$, where $M$ is the length of a block in bits.

The number of permutations of $n$ different objects is $n!$, so for our (very unpractical) block cipher, there can be at most $2^M!$ keys. Many of those will be unusable in practice (for some, plaintext and ciphertext will differ for only a single block), but they all satisfy your condition that they differ in at least one plaintext-ciphertext-pair from all other permutations.

Now, specifying one of all possible permutations without any optimization would take an insane number of bits to transfer (the number of plaintext-ciphertext-pairs in the permutation, times the number of permutations: $2^M\cdot2^M!$

To be able to actually transmit the key with fewer bits than any conceivable message, we limit our keyspace to mere $N$ bits, or $2^N$ possible permutations.

If you insert the actual numbers, we get $2^{256}$ possible keys for AES-256, which seems like a lot (and for practical purposes, it is), but the theoretical limit for 128-bit blocks is much, much higher: $2^{128}\cdot2^{128}!$.

Update:
Avijit has pointed out in the comments that there is an easy optimization which allows enumerating all possible permutations with "only" $\lceil log_2 2^M!\rceil$ bits (which allows for $2^M!$ keys). This is a lot more compact, but still much larger than any practical key size.