There are two variations of this question:
First, we have two objects that are travelling in opposite (i.e. directly towards each other or directly away from each other). If we want to calculate relative velocities, we ADD their individual speeds.
Second, we have two objects travelling in the same direction (usually a catch-up question, like the one you posted). If we want to calculate relative velocities, we SUBTRACT one speed from the other.
So, in this example, the cyclist gains (20) - (4) = 16mph
5 minutes is 1/12th of an hour, so in the 5 minutes of travel the cyclist travels an extra 1/12(16) = 16/12 = 4/3 of a mile.
At a rate of 4mph, it takes (4/3)/(4) hours (4/3)(1/4) = 1/3 of an hour (or 20 minutes) to catch up.