Keep in mind your goal is to make their lives interesting, to YOU. Some ways I might do it if the PCs were set up to be a band of vicious and heartless raiders, personally:
See how far they're willing to go. You can just ask this when they open their mind to the world's psychic maelstrom, or put it into practice. This innocent camp of defenseless people, whose warriors all got wiped out a few years ago fighting off the last batch of raiders? What about this holding full of sick and starving diseased people, that barely have anything worth stealing?
Give them a challenge. A warlord with a fortress of stone and metal and a well-armed gang of vast size, and you don't have enough food to just wander off into the wasteland and find another target. Or maybe a less well-defended holding, but there's another band of raiders going after it, too: can you fight them off without destroying the prize you're fighting over?
Barf forth all the weirdness of Apocalypse World. Raiders have to deal with the fact that weird shit like Brainers and Hocuses, Perversions of Birth like Blind-Blue, Breeding Pits, Mutants, etc. And the World's Psychic Maelstrom, always there, always waiting for you to open up.
And if you've got a Chopper (or a Hocus, or an Operator, or anyone with a gang or crew improvement), man, use those NPCs the way the game tells you to. Name them, make them human, and then use them for PC-NPC-PC triangles before you put them in the crosshairs. And invoke their stuff's downside: If they don't have a savvyhead, where do they go when their bikes need maintenance? If they don't have an angel, what do they do when somebody gets sick? Things they'll need to find the services of an NPC for? It's a little bit complicated to just ride in, grab who you need, tie them up, and procure their services at gun-point.