The asymmetry between NPCs and PCs is an important part of the game. It's a
mechanical asymmetry. The thing is, PCs roll, so they need stats. You can have an NPC be anything you like -- you're the MC. "Classes of their own" -- well, they sort of already have "classes" -- threat classes: Warlord/Alpha Wolf, Brute/Sybarite, and so on. You can give them moves, too, but there are two types of moves -- MC moves, which are just "reminders to the MC to do something", and don't have mechanics (so like "reveal the secret beneath the caves" or "summon the nanite swarm" would be MC moves relating to a specific NPC), and PC moves. You can create PC moves tied to a specific NPC, but the PC still rolls. ("When you're attacked by the nanite swarm, roll+weird. On a hit...")
So you can make your NPCs be anything you want, but they don't look, mechanically, like PCs. They look like threats, because they're yours.
If you want to give them more harm levels you can, but remember to look at everything that's yours through crosshairs. Ask yourself, why do you want this NPC to be physically hard to kill? That may sound like a silly question if you're used to games where killing the level-boss monster is a matter of whaling away with attack after attack, chipping away hit points while surviving its attacks until it succumbs to attrition. But AW is designed to avoid that kind of lots-of-the-move-in-a-row battle, because it's seen as kind of boring. (Even Dungeon World, which is AW hacked to a classic D&D setting, avoids this: cf.
http://www.latorra.org/2012/05/15/a-16-hp-dragon/ )AW is much more about a volatile situation with no status quos. Want to kill the big bad NPC? Ok, he's dead. Now you have to deal with the consequences of that. Maybe they're even worse. This is not to say that there's never an NPC who's hard to kill, but usually it's more interesting than "he just has a lot of hit points". It's more that he's hard to get at, that achieving the fictional positioning required to be able to make that seize or go aggro move is the hard part. Maybe his gang's in the way, maybe he's got leverage which makes taking him out dangerous, maybe he has a custom move -- "Rudder always knows you're going to hit her a few minutes before you do. When you seize or go aggro on Rudder, roll+sharp. On a 10+, you've managed to fool her about exactly when or how, though she still knows it's coming; go ahead and do the move, but take -1. On a 7-9..." and so on.
You can certainly customize playbooks (technically, you're either adding PC-specific custom moves to your homefront, or starting your own mini-hack, either of which is heartily encouraged) but, again (and as noclue said), think about why. Might be worth playing with the constraints of vanilla AW first. Might be that you can achieve what you want with the playbook and its advances. Might be that you can achieve it in the fiction (maybe the Driver ought to go
take that tank, on table, away from whoever's currently got it).
The examples in the rulebook do highlight a lot of merciless PVP that gives you the sense that everyone is an asshole to each other, but I think play is most interesting when there's a mix of assholery and not-assholery. Characters who are simply all perfectly loyal to each other, and characters who are simply constantly amorally out to screw each other, are both more limited a scope for story than characters who have urges that both unite and divide them. Vincent is on record somewhere saying that he expected AW PCs to interact like the characters in Firefly -- at each other's throats a lot of the time, but always ready to unite in the face of greater dangers. The campaign I've been running is more PVP than that, but still with plenty of room for alliances and morally-gray antihero moments of selfless nobility.
As for what the maelstrom is and can do, and what happened to the tech, and so on, for one thing, what noclue said -- ask the PCs. But also, maybe the PCs don't really know that much, maybe it's a mystery to them too -- they live in the presence of the maelstrom and make some accomodation with it, but don't know what it's actually capable of, or what the hell happened. I suggest you play to find out. That means it's an emergent result of the characters' actions; neither the players, nor the MC, knows going in. The rules say you find out what's beyond the maelstrom when a character takes advanced open your brain and hits a 12+ -- and, the rules say, "I envy you finding out."
Check out this thread:
http://apocalypse-world.com/forums/index.php?topic=6587.0 for a discussion of various takes on the maelstrom and on playing to discover what it can do.
(Interestingly, my take after reading the rulebook was not "where did all the tech go" but rather "50 years out, why is there so much left?" Biker gangs with ample gasoline, ammo to spare, cans of peaches, violation gloves in working order? Hardly anyone I know IRL knows enough to make a bow and arrow, never mind maintain a motorcycle without an international supply-chain for parts. If our current house-of-cards technological society collapses, I'm imagining a lot LESS tech 50 years out....)