Reflecting and radiating heat are mutually exclusive, and if some material is good at radiating heat, it is also good at absorbing heat, otherwise it would violate the laws of thermodynamics.

It is a bit more complicated than that because light come in different wavelength, but it is the general idea.

Railroad rails tend to be dark except for the polished top surface, so they absorb/radiate the heat more than they reflect it. Painting them white changes that, it makes them less effective at radiating their own heat, but because they don't produce much heat by themselves, it is not a big effect, but it also makes them less effective at absorbing the heat from the sun, a much greater effect, so, the rails get cooler overall.