Russulas, for instance: in my country, there are no poisonous ones, but there are at least 90 varieties and experts will often need DNA analysis to place them confidently. The procedure for determining edibility recommended by the foraging association is, once you're certain it's a Russula, to taste a small piece and spit it out. If it has a burning sharp taste, it's not food.
The app has been very good at predicting whether I'll experience that burning sensation, and all from signs that are invisible to systematic description (I won't rule out that an expert can also spot subtle differences between a sharp green russula and an edible green russula, but they probably wouldn't be able to describe it).
iNaturalist or Seek by iNaturalist? I didn't think iNaturalist had an identification method other than "wait for an expert to come along and tag your photo".
Seek, on the other hand, is happy to make up identifications itself.
I have not tried Seek, but also just know to double check any iNat recommendations when I get home if I’m not 100%.