So every employee in every line of work needs to know all of OSHA rules. How are the people that work in a small office building that has no maintenance staff going to ever know of 70E and the fact that there may be rules that need followed just to turn on a 120 volt circuit breaker? You are exposed to similar risk just plugging in a copying machine - especially if there is a fault in the machine.
First, people need to know the rules that apply to them. Employers need to know what rules to tell their employees.
Second there is nothing in NFPA70E that says what PPE is required for 120V office equipment, nor for light switch use, nor for switching small molded case circuit breakers.
OSHA says you as an employer, need to identify hazards in
your workplace and protect your people from them. NFPA70E focuses on electrical hazards.
NFPA70E has some tables that can be used in place of an analysis when performing specific task on electrical equipment in a manner that may cause an arc flash or exposed workers to electrical shock. If you use these tables NFPA70E includes suggested PPE.
If you decide to perform some risk analysis and decide no hazard exists, you may need to argue your position in a court of law or before an appeals board. But you are free to do so.
If you decide some risk exists and you choose to perform calculations, you are then free to choose whatever PPE is required to protect you from the specific identified hazard. While it is extremely convenient to use the 70E PPE tables, they are only required when using the 'task tables'