You didn't state; are you going to be setting up a PM system for the building systems like HVAC, air compressors, boilers, phones, networks, etc, or just the process equipment?
Expanding on what mburtis said; inventory every asset (equipment) that you will be responsible for. Determine the criticality of each asset and rank them in maybe 3 categories, A,B, and C. A rank A asset is one that is absolutely critical for plant operation. Size is not necessarily a factor here. It can be something as small as a fractional HP feed pump or mixer that if failed will shut the whole operation down up to a motor of hundreds of HP and their associated control and starting components. If there is already a redundant back-up asset in place like 2 or more pumps that pump into a common manifold and the system will operate without one, this is not a rank A asset. These are the items that should get most of the PM activity.
Rank B assets would be ones that are mostly an inconvenience if failed, ones that would not shut down the entire operation. Also look at what collateral damage would be caused if a B rank asset failed; if it's like a coolant pump and would eventually take out an A rank if it failed, it too would be an A rank.
Rank C assets would be "run to fail", and not really worthy of much PM attention.
You mentioned looking for documentation for past breakdowns, might be a good time to recommend a CMMS system. They are expensive and you will get push back from management because of the cost and push back from the maintenance crew for having to use it. Once set up and breakdowns start being documented in the database, they can be quite valuable for identifying the problem children and repeat offenders.
Inventory your PPE as mentioned before, do you have blast suits, kevlar jackets, gloves, etc? Inventory your tools; in addition to all the meters, a thermal camera and motor circuit analyzer are extremely valuable. They both require some operator training, but can be invaluable in spotting potential problems before anything fails.
Inventory your human assets, how many guys are trained and competent to work on how many different assets? Avoid the pitfall of only having one guy that can fix a specialized asset. That guy will take vacations and may even have some sick leave. Establish competency levels and level up the training for other guys.
This part is painfully slow, but needs to be done. Establish critical spare parts for rank A and some rank B assets. Buy the parts and set up a stores system to ensure they are on hand if needed. Pay particular attention to any OEM part that is imported, they can take months to get in.