Atomic emission spectroscopy of turntable electrode (RDE-AES) is widely used in oil detection because of its simple operation, no need for sample preparation, and high reliability. However, the arc is the primary light source used in this technology. The instability of the arc caused by the change in the discharge gap induced by electrode wear and other factors leads to errors between the analysis results of the last collected spectral data and the actual situation. Herein, a method using atomic emission spectrometry with an oil detection device based on the “double turntable” electrode structure is proposed. In other words, the rod electrode in the traditional “rod turntable” electrode structure is replaced by a turntable electrode that can rotate. Its significant advantage is that it reduces the detection error caused by electrode wear. For its structural physical modeling, the process of arc excitation is simulated by COMSOL multi physical field simulation software. Further, the changing rules of electrode gap, oil film thickness, and external excitation on the arc excitation effect are explored using the control variable method. The effects of the influencing factors on the arc excitation time and instantaneous excitation temperature are obtained, and the parameters are optimized according to the simulation results. The simulation results show that the excitation effect of the “double turntable" electrode structure is significantly improved compared with the traditional structure, and the excitation time and temperature are improved to a certain extent. In particular, the arc excitation effect is stable in mass testing, which verifies the progressiveness and practicability of this method. It also provides analytical support for in-depth research on oil detection using the method based on turntable electrode atomic emission spectrometry.