The use of the Perfective depends on the context, just like Tati said.
You asked "how should I approach verbs that have more than one perfective form? "
1) You approach them just like any other aspectual pair, one by one as you study your functions of the Perfective.
2) Then, the contexts for the Infinitive, Imperative, Past , and Future are different and should be approached separately.
3) Also, Perfective of Verbs of Motion should not mingle with the regular verbs.
your example, ЕСТЬ - поесть / съесть is a great example. The choice is clear in both Infinitive( я хочу есть or я хочу поесть) use,past (я поел or я ел ), Imperative (съешь, поешь),and the Future (Я поем/ я съем). Unfortunately, it's not as obvious for all the verbs, as the semantics of the verb itself also plays its part.
Have fun!