Relative velocity is the sum of the vector velocities acting on an object from a frame of reference
B to Car A is 100 km/h - 75 km/h = 25 km/h
If the velocities are in two different directions, then they can be added/subtracted like any vector
The velocity of object A relative to object B is the opposite of the velocity of object b relative to object A, represented by vBA = -vAB