Here are videos showing two different traditional ways of making indigo dye from P. tincoria with some simple explanation of the mechanism.
The Japanese awa-indigo use fresh green leaves. The chopping and bruising disrupt celluar compartments and the indigo precursor reacts to enzyme and oxidizes internally. After oxidative decomposition similar to hot composting, part of the plant tissues break down and gases off, the volume reduces. The residues then undergo anaerobic fermentation in alkaline solution. Metabolism from bacteria provides reducing power and releases indigo from insoluble complex into the liquid for dyeing.
Liziqi's "life of the bluegrass"
This is the traditional Chinese way. Older plants are harvested and soaked in water to partly break down plant tissues. Indigo precursor and enzyme are released and the resulting indigo remains largely in the soluble reduced form. It then is oxidized by aeration and precipitated by calcium (quick lime or hydrated lime). The blue mud or paste is retrieved and stored. Reducing power comes from rice wine culture. Various fungi break down starch to sugar and ferment it into alcohol as the reducer.
From my experience, if green leaves are soaked anaerobically too long, the indigo binds to chlorophyll and probably other hydrophobic molecules as well. The precipitation is not as pure and has a green tint. Those impurities make subsequent reduction and solublization difficult. So what I have experimented is to find the sweet spot of leaching condition in which there are maximum indigo precursor, some enzymes, and minimum chloroplast. Then I proceed to use common household chemicals and utensils to extract the pure indigo. It can be an overkill for simple dye project but it's fun.
I have no experience with the legume Indigofera. tincoria as it needs warmer climate to grow. It seems the extraction is much simpler with this plant. Oxidized indigo just associates with the foam on top of the water in large quantities, making collecting easy. I guess it contains higher surfactant than other indigo plants.
Traditional woad processing is somewhat similar to sukumo. Woad leaves are kneaded and balled for slow fermentation. I still can't find the way the extract indigo from fresh leaves. Maybe the yield is just too low.