Ask yourself one simple question about your characters: Why don't they fit the role that they've been put in? (and put the worst person you can think of in that role)
This works because friction between a person and their position generates story for free. A character who fits smoothly just executes the plot; a character who doesn't fit has to improvise, apologize, overcompensate, or bluff, and every one of those reactions reveals who they actually are. Say your story needs a diplomat to broker peace between two rival families. Don't pick the smooth talker — pick the family's most hot-tempered, tactless member, the one who once started a fight at a wedding. Now every negotiation scene crackles, because success requires them to fight their own nature.
The caution: mismatch needs a reason and a limit. If everyone is comically wrong for their job, the world stops feeling real and starts feeling like a running gag. Save the worst-fit casting for the roles the story actually turns on.
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