Shortest paths are representative of discrete geodesic distances in graphs, and many descriptors of networks depend on their counting. In multiplex networks, this counting is radically important to quantify the switch between layers and it has crucial implications in the transportation efficiency and congestion processes. Here we present a mathematical approach to the computation of the joint distribution of distance and multiplicity (degeneration) of shortest paths in multiplex networks, and exploit its relation to congestion processes. The results allow to approximate semi-analytically the onset of congestion in multiplex networks as a function of the congestion of its layers.