It can be a bit complicated. There are actually two isolation between pairs of cables, one is call near-end cross-talk and one is called far-end cross talk. For near end, if you have a pair of cables, you inject signal into one of the coax pairs, loads on the other end of both, and measure what comes out of the near end of the other coax. It is an S21 measurement. Far-end is similar but you put the VNA port 1 into one of the cable inputs, and a load on the other; then you put a load on the cable far-end of the cable that has port 1 going into it, and you connect port 2 of the VNA to the other cable (which has a load on the near end), and measure S21.
If you are measuring differential cables (that have two-wires, often twisted together) it gets a bit more complicated.