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Headcanon thread? I'll start:
Evil team grunts aren't really as stupid as they seem; they're trying to help out the protagonist.
In Giovanni's case they fear punishment out of a brutal mob boss and so they figure they can dodge that if this kid somehow manages to take him down.
Team Aqua and Magma grunts might not have realized upon signing up just how fucking insane their bosses' plans were, so now after fulfilling the barebone minimum duty that they signed up for they try and help Brendan/May take down these idiot madmen. After all, you don't really think they'd just keep a Master Ball on display in their hideout, right?
A similar case with Team Galactic. 'Join an evil team and get money and take over the world' sounds great in practice, but when you've got this crazy nigga tearing open a hole to another dimension and Giratina the Death God comes roaring out of the portal the idea suddenly seems a lot less appealing and they want out.
(I have nothing for Plasma or Flare because they kept their true intentions hidden pretty much until they actually acted on them.)