It has to do with hydrophilic vs phobic substances. Most spicy things are hydrophobic so trying to wash out with water does absolutely nothing basically.
I always thought that spicy foods was acidic (as that’s what made them spicy) and milk was an alkali so it neutralises the acid making it less spicy, I may be wrong.
Also Krysyy you can live up to being the red dragon now :p
Capsaicinoids are slightly basic in solution and nonpolar. Milk is slightly acidic (lactic acid) but not enough to do much. Because capsaicin and similar are nonpolar, water (polar) will not readily dissolve it them.
This means it will either do nothing, spread it further around the mouth/throat making it worse, or at best flush it from the tongue so it's not as bad. Milk has polar and nonpolar substances in it. The nonpolar bits will more likely dissolve the spice and get flushed away with the rest of the liquid.
The problem is still that spice is stuck to your taste receptors. If this bond is stronger than soluble forces, little will be dissolved and all you managed to do is drink milk without solving the problem. The coolness or taste of water/milk may still provide relief to the receptors, but the fire will linger.
To get rid of the fire, I recommend drinking olive oil or eating peanut butter, alcohol that is of a high percentage, or to eat some sugar (the Scoville scale is based on the amount of sugar needed to dilute chili).
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