In this paper, a nickel-based amorphous composite coating was obtained on the carbon steel surface by the laser cladding process. The thermal field and stress distribution were simulated by using ANSYS finite element software where the moving heat source and powder feeding were modelled by the “Element birth and death” method. The simulation results were verified by comparing the cross-sectional profile of fusion lines and X-ray stress measurements, respectively. The results on thermal field showed that the cooling rate of the coating could reach up to 10389.15 K/s and it gradually decreased from the outside surface to the interior, which promoted the formation of amorphous phase. The simulated stress field showed that the coating was in the state of tensile stress after cladding and the longitudinal stress was larger than the transverse stress. The coating was experienced with tensile plastic deformation along the laser scanning direction, which resulted in longitudinal residual stress. A higher stress concentration was occurred between the coating layer and substrate, which increased the susceptibility of crack formation. The test results on transverse residual stress were generally consistent with the simulation. On the contrary, the measured longitudinal stress was nearly close to zero, which was not in agreement with the model due to the formation of cracks.