You are correct on the frequencies and the input. Channel 1 is car to car, simplex, direct what ever you prefer and channels 2 thru 5 are the repeaters which start at Humpback Rocks as channel 2, next one south bound is channel 3, then 4, then 5, then back to channel 2 so forth and so one. They changed unit numbers a few years back due to restructuring. The 100's are park admin, the north district LE units begin in the 200's, from Roanoke to the NC line they are 300's, 400's are the next district, then 500 and 600 finish at Asheville. The maintenance people when assigned to a certain district, say district 3, seem to be the 350's and 360's. Most LE units are say 301, 302 district supervisors, 310, 311, 312 would be rangers in district 3 area or zone 1, 320 district 3 area 2, so forth and so on.
As for the PL tones on the input frequency (166.375) I think they are 110.9, 114.8, and 123.0 but I cannot confirm. I do know 103.5 is the tone for 167.175. Leaves will be changing soon, and you know what that means, heavy traffic.
Hope this helps,
David Hartman