The optical rotational Doppler effect (RDE) is closely related to the unique orbital angular momentum (OAM) carried by optical vortex, whose topological charge means the mode of OAM. Compared with the coaxial incidence, the rotational Doppler frequency shift spectrum of a misaligned optical vortex (misaligned RDE) widens according to a certain law. In this paper, an OAM modal decomposition method of the misaligned optical RDE is proposed and the relative intensity of different OAM modes, namely the OAM spectrum, is derived based on an inner product computation. Analyses show that lateral displacements and angular deflections change the distribution of OAM modes relative to the rotation axis of the object. A misaligned Laguerre-Gaussian (LG) vortex can be represented as a specific combination of coaxial LG modes, and the difference between the topological charge of two adjacent modes is 1 or 2 with lateral displacements or angular deflections respectively. An experiment of misaligned optical RDE using a superimposed LG vortex is executed, and the obtained frequency shift spectrum with misaligned incidence expands into a set of discrete signals, which agrees well with the theoretical results. Moreover, we can get the rotation frequency of the object from an expanded frequency spectrum more quickly and accurately based on the difference between two adjacent signal peaks. The proposed method contributes to analyze the misaligned optical RDE comprehensively, which is significant in remote sensing and optical metrology.