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They're kind of two different games.
Hive War lets you play inside the Underhive, with no vehicles. The game works best with lots of terrain, a lot more than you will get in the Hive War boxed set.
Ash Wastes is out in the wasteland, using vehicles. It's essentially an expansion for Necromunda.
Regarding the rules, I don't own Ash Wastes but from what I hear it's a pretty comprehensive book, whether you're playing in the Underhive our outside of it. The Hive War rulebook is fine for learning but it is missing key information, like how to play a campaign. You will want to pick up a more comprehensive rulebook at some point.
Remember that Ash Wastes is almost twice the price of Hive War. Sure, it's a more comprehensive box but it's only really worth getting if you want to get into the vehicle side of Necromunda. If you're happy to stay in the Underhive I'd get Hive War and see if you can buy a separate copy of the Ash Wastes rulebook. You can also buy the hardback Necromunda rulebook, but even that is out of date now, the Ash Wastes rulebooks contains corrections.
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