I think the solution is:
Line by line:
My beginning: steamy, but 2/5ths crazy
As GrumpyLlama59 noted, this is cluing LOCOmotive (which is the front of the train, and the caboose is typically at the rear). It's somewhat of a red herring because it's talking about the physical beginning rather than the word's beginning.
My middle, wailing, from spectres hazy
Ghosts say BOO
My end, demonic, lives in Hell
OSE is a demon and the "Great President of Hell"
My start, to there, does transport sell
A mode of transport you pay for is a taxi CAB
My middle, within, the original man
Possibly, cABOose => ABOrigine (meaning original inhabitant)
My end, ends, an ender of lifespan
A nOOSE ends lives (from OP in chat)
Hint #1: All shall fear my reflection
Next few lines are based on the reverse of the word: ESOOBAC
Its start starts matters of perplexion
ESOteric things are perplexing
Its middle lives beyond the pale
Something "beyond the pale" is outside normal boundaries, or "Out Of Band/bounds"
Its end is my start's last tale
High BAC (Blood Alcohol Content) would be a CAB driver's last tale, either because of an accident or from losing their job (from OP in chat)
Hint #2: ...
The line about "skulls, stopping, cackle and grin" is referring to the high mortality rate of the brakemen working in the caboose (from OP in chat). The rest is clarifying that the "beginning" (locomotive) is not the same as the "start" (cab...) and that Hint 1 isn't a real word.
Hint #3: My beginning runs so desperately / From me why does it always flee?
Talking about the locomotive/caboose relationship. The locomotive is always "running away from" the rest of the train, which is being pulled along behind.
My ends, each two, letters in sum / Are a mystery and madness to succumb
Two letters from each end, concatenated => CAbooSE => CASE => both "a mystery" (as in a police investigation) and "madness to succumb" (as in headcase or basket case)
Hint #4: My letters are of number seven / Ask for more hints and I'll send you to heaven
Indeed CABOOSE has seven letters
Title: I terrify those beneath
OP confirmed in chat that this was to set tone/theme of terror, literally referring to being run over by a train (though I'd argue that taking the slang usage of caboose => buttocks would terrify anyone trapped beneath too).