Since each passenger has equal probability of choosing any of the stops, we need only take the number of desired configurations over the number of possible configurations.
There are $4$ choices to make in order for all passengers to exit the train (each must choose some stop), and $6$ options for each, so there are $6^4$ total arrangements in which the passengers can exit the train. If you like, think of it as each of the $4$ passengers rolling a distinctive $6$-sided die, and getting off at the stop that their die indicates. There are $6^4$ ways to roll $4$ distinct $6$-sided dice.
There are ${}_4C_2=6$ possible ways we can choose the first pair to exit (and the first pair determines the second pair, so there's nothing else to do. There are ${}_6C_2=15$ ways that we can choose two stops for our pairs, so there are $6\cdot 15=90$ ways that the passengers can exit the train in two separate pairs.
Hence, the probability is $$\frac{90}{6^4}=\frac{2\cdot 3^2\cdot 5}{2^4\cdot 3^4}=\frac5{2^3\cdot 3^2}=\frac5{72}.$$