I've worked previously as a firefighter, a lot of the stuff that we do can be considered high risk. PPE is incredibly important however there are several issues I have noticed while working with PPE.
1. PPE can get in the way of being efficient.
From personal experience this is one of the most painful things. Engineers design equipment to meet requirements. The people setting these requirements are often bureaucrats who have no knowledge of what it feels like to be doing the manual labor. Some of them may never have even handled any heavy machinery in their life - the end result is you end up with unergonomic tools. Since, the workers are not the ones paying for the tools, the upper management will select things that hit their own KPIs. Some how you are expected to hit unrealistic throughputs with tools that dont work well with your PPE. End result is most people will neglect PPE and find ways around it.
2. PPE upkeep
One has to keep equipment in good condition. Using boots with holes is not going to be a good idea. Corporate culture however is such that they make replacing PPE very painful, in part because PPE is ridiculously expensive in certain contexts. Good managers and supervisors will make sure their crew has safe equipment but often have to take the blame if they overspend. Lazy managers/supervisors will make it a nightmare if anything gets damaged. Unfortunately the number of lazy supervisors far outstrips good supervisors. This can result in things like black markets for PPEs.
3. Workplace culture
It can be "manly" to do things in an unsafe manner. This takes a lot of work to solve but the best way to solve it is by trying to inculcate a culture where people don't cause suffering for others just because they suffered. There is no need to "pay forward" a malpractice. If someone abused you earlier for conforming to something, that doesn't give you the right to abuse your junior. The problem is people who do this kind of change often go unnoticed.