Don't substitute random shit like naptha, acetone etc. Just go out and buy some methanol. It is not controlled. People use it as brake line de-icer, or as a fuel for camp stoves.
There is no need to use denatured ethanol, acetone, naptha, ethyl acetate, dichloromethane, hot water, ether, petroleum ether, diglyme, toluene, PEG 400, isopropanol, butanol, butyl acetate, isopropyl myristate, dimethylformamide, DMSO, acetic acid, propanoic acid, or anything else.
Use methanol. It selectively dissolves the psilocin and psilocybin and leaves everything else behind. Put chopped up mushrooms in methanol. Warm the methanol gently, with a warm water bath. Keep it warm for 2-4 hours. Drain the methanol. Let it evaporate.
You can recrystallise the psilocin/psilocybin from a small amount of boiling water if you are concerned about ingesting traces of methanol. But you'd ingest more MeOH in a typical glass of fruit juice than that trapped in crystals of psilocin.
Again, don't substitute anything else. Just use the damn methanol. Anything else is going to be more difficult to use, less selective, or more expensive.
footnote: you can use ethanol if you're desperate, but it will take longer to evaporate.