Why?
as someone from reddit told me
"Probably go shrooms first because they hit you up with the real no nonsense deal, you will freak out, you might cry, but you will thank the fungus when you are done."
i tried shrooms first, and to this day i do not regret it. i'd even go so far as to say it changed my life.
shrooms first if you want the natural psychedelic experience, then acid, DMT, peyote, or whatever else. just trust me on this. i did shrooms first and it was a really really good choice.