Quantum control techniques play an important role in manipulating and harnessing the properties of different quantum systems, including isolated atoms. Here, we propose to achieve quantum control over a single on-surface atomic spin using Landau-Zener-Stückelberg-Majorana (LZSM) interferometry implemented with scanning tunneling microscopy (STM). Specifically, we model how the application of time-dependent, nonresonant ac electric fields across the STM tip-surface gap makes it possible to achieve precise quantum state manipulation in an isolated Fe^{2+} ion on a MgO/Ag(100) surface. We propose a protocol to combine Landau-Zener tunneling with LZSM interferometry that permits one to measure the quantum spin tunneling of an individual Fe^{2+} ion. The proposed experiments can be implemented with ESR-STM instrumentation, opening a new venue in the research of on-surface single spin control.