I’m pretty sure BLAS will tile out the matrix multiplication internally anyway, so it doesn’t matter. At least for matmat would, is matvec special?
However matmat is done, row-major vs column-major for both matrices shouldn't make a difference (for square matrices at least).
I don't know if tiling is done for matvec. I don't think it makes sense there, but I didn't think about it too hard.
For the row-major layout the multiplication Ax ends up being more cache-efficient than for the column major layout, as for calculating each component of y you need to scan x and a row of A.