What's your life worth?
Two items that NFPA 70e addresses: Shock and Flash/Blast.
Flash PPE is designed to make it so you may survive an incident with SECOND DEGREE BURNS, you will survive but be badly scarred and in quite some pain, if you have at least the minimum PPE for the known incident energy (You have calculated this or know what it is for each piece of equipment, correct?). If you have never experienced copper plasma, count your blessings and do all you can to make sure you are not involved in an incident, it will be a significant emotional event in your life. Mine occurred 10/17/1997.
Shock is not as "glamorous" as flash but if you can't let go of the live circuit, you can die. The gloves are to help minimize your chance of shock. How much current can be fatal? Less than 50 mAmps, and few of the circuits are fused this low. Without PPE, it's like Russian Roulette, are you feeling lucky today?
The law was created because too many people were having accidents. It has reduced electrical accidents significantly since it was enacted. I agree it seems a hassle to "suit up" every time you are above 50V but just two weeks ago I went into a "safe" 60 A disconnect that actually went straight to a 600 A 480V substation circuit breaker as it was not wired per the building's electrical drawings. Was I ever surprised and glad I had followed our company's policy when I measured 277V from phase to ground.
Sorry for the rant, I was at one time of the "it can't happen to me/ it's too much of a hassle" group but have seen the light.
ps. Don't forget the hearing protection when you suit up, my ears still ring occasionally from my event.