The electrostatic accelerometer is the key payload of many space missions, such as satellite gravity measurements, space gravitational experiments, with a typical precision requirement from nano-g to femto-g. The measurement error model analysis is an important issue for the electrostatic accelerometer with numerous error sources. The traditional method by theoretical analysis is complicated to evaluate the complete measurement error models quantitatively especially when the machining and assembly errors of the sensor head are considered. Limited by the earth gravity and seismic noise which is much higher than the intrinsic noise, the complete error model of electrostatic accelerometers can also hardly be tested on ground. In this paper, the method by using finite element analysis of the sensor head is studied. The simulation model for an electrostatic accelerometer sensor head is built, and the multi-conductor capacitance matrix data is simulated. The accuracy of the capacitance simulation is evaluated in three ways including the convergence check of the capacitance with the mesh size, the symmetry verification, and the sensitivity comparison with the theoretical model. Finally, the accelerometer measurement model is analyzed based on the simulation data, using the case of rotating installation misalignment of the upper electrode as an example. The measurement model and error items of one horizontal axis and one rotating axis are quantitatively evaluated. The method proposed in this paper provide a new effective approach to the measurement model analysis of the electrostatic accelerometers in complex working scenarios both in orbit and on ground, which could be helpful to enhance the performance and the efficiency of application.