Start with 2-1.3.3.3 to see how to identify the required PPE. This section details the two ways to identify the required PPE for a task.
The first is as you suggested, find the task in Table 3-3.9.1 of NFPA 70E-2000 and note the hazard/risk catagory. Then go to Table 3-3.9.2 of NFPA 70E-2000 to find the PPE required for that task. This is a general table and I can see where some instances are conservative and others may be inadequate. It all depends upon the available fault current and the overcurrent device and operating time that is protecting the circuit.
The other way is to calculate the incident energy available based upon a selected working distance. The FR clothing and PPE used must be rated for this amount or higher value of incident energy.
