The more unorthodox extended playbooks would be the Child thing and Quarantine, because they bring some immediate impact to the fiction, with the wolves and memories, but they aren't super-crazy like some of the first edition ones (Solace, Maculoso,etc). They aren't more challenging to play, but explain how they work since they don't have that little explanation the core ones have. The Show's pretty nuts but is probably easy to play since it's pure Id.
Something like
The Faceless: Unstable even by apocalyptic standards, the Faceless is a very scary opponent to be around. Remember that you've got some very powerful and +Weird moves, but not the stats to make them reliable. Just think about what's really under your mask.
The Quarantine: An awoken survivor from before the apocalypse, your greatest strength is that you're sane, ethical and belong to a better world. These are also your greatest weaknesses.
The Waterbearer: A leader in control of something precious, and in charge of protecting it from the evils of the world, but without much direct power. Try to stop the world dragging you down to it's level.
The Child Thing: The creepiest fucker in the book. You're going to need to rely on your smarts and weirdness to protect yourself from the wolves, unless you can drag the adults into the hunt.
The News: A social powerhouse with a great sway over the public, but beholden to those above you for barter instead of those beneath you. Decide how important the truth is to you.
The Show: Ruin everyone's lives by being really fucking metal. Remember that all the consequences for cracking open the world are going to get everyone in a lot of trouble.
I had a new player go Quarantine, and it worked pretty well for them. It's a fairly approachable archetype because you don't have to go hard into Crazy Apocalypse Asshole (which is half the fun but whatever) It was a bit of an odd dynamic though since a couple of players set up pre-apoc survivors and were fairly friendly with each other. It's not an especially complicated character to play, just keep an eye on the Start of Session and income rules since they've got some important ones.