Is requesting O&M to send you to a class an option?
If you are talking safety of maintaining and operating, consider hiring a specialized outfit come in and train you and your staff. Specifically, you can inquire with the manufacturer of the 4160V switchgear in your plant and see if they provide training. I bet they can refer you to someone, too. This will be far more effective than reading anything someone here can easily link to you. Don't get me wrong there are many smart and experienced folks here and they can give you pointers, but if the focus is going to be the safety of working with the medium voltage at your plant, you need someone to show you, not tell you. Also, the training needs to be tailored to the electrical system you have. I cannot recommend strongly enough to have a safety and training outfit evaluate your electrical distribution system and identify the risks and potential fixes, then train you on safely operating and maintaining it.
In summary, there are so many considerations that depend on your current skillset, plant, coordination of OCPDs (or lack thereof), resources, SOPs, PPE and education, it's impossible for me to confidently suggest anything. Medium-voltage is extremely dangerous. This cannot be understated!
Another critical consideration is arc flash, an entirely different subject in itself and also depends on what you have installed and its maintenance history.