You must first...
...identify and assess any hazards and risks to the health and
safety of anyone in the workplace (because different tasks will
require different equipment).
Put into place primary measures to reduce these risks to an acceptable
level.
Before...
...identifying appropriate PPE.
For Example...
...an engineering company should fit screens around a lathe as
the primary protection, and provide individual eye protectors
as the secondary protection because the screens will give more
effective and consistent safety for everyone.
Once you have decided that PPE should be provided then you must
ensure that it is used properly at all times the risk is there.

When
does PPE have to be worn?
Simply whenever the risk is present.