You wait until they pair up and see which one lays the eggs and which one makes runs over the eggs. Otherwise you can only guess. Some are better at guessing than others, discus Hans is pretty good at sexing but he will admit its not a science
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It's difficult, and no particular physical aspects are anywhere near 100% accurate.
I have identified a few pairs (that actually went on to spawn) by noting that some (mature/adult) males' dorsal fins can be somewhat pointed upwards in a slight arc at the very back end, whereas in the females it tends to be quite rounded and even, with no upward pointy end.
Far from 100% accurate, but a good guesstimate might be 60% or so.
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