"Who" refers back to "people," so use a plural verb. Multiple people know how to operate the equipment!
Don't be distracted by the singular elements: (1) Martha, (2) "is," and (3) "one." Yes, Martha is singular, but she already has her own verb: "is."
The word "one" is a subject complement, modified by the prepositional phrase "of the few people." The relative clause "who know how to operate the equipment" modifies "people."