From my experience facing teams with poe on the starting lineup, he will attack anyone with his special...even ships with full protection.
The ai does not use him well and he is too squishy to be a good starter.
However, as a reinforcement for defense, many ships will have lost thier protection so he has a better chance of lne shotting someone.
And as Kyno correctly said, for offense, always use poe buff first because even a nearly maxed poe will not always 1 shot tfp.