Question for the people who have used the CH32V003 or more generally WCH, either for hobby or production, what is the current state of documentation and toolchain for these chips? Positive experiences, war stories?

I've used CH32X035 (which is practically CH32V00x plus USB and some other things) at the hobbyist level (no-frills keyboard PCB designs).

The impression I get of WCH and their CH32 line is it ... draws heavy inspiration from STM32.

WCH provide English translated datasheets and reference manuals. They're fine.

Their own recommended toolchain is a fork of GCC. But as far as I can tell, they haven't shared their changes anywhere. The specifics of the changes they've made are a bit beyond my understanding, though.

With the open source distributions of GCC toolchains work just fine. I've built Rust crates as firmware libraries for them.

That the CH32X035 is very simple to design for (& low cost) means I'd rather make use of it for hobbyist keyboard PCB designs compared to the RP2040.