Vinyl ester (VE) resin has strong environmental tolerance and is the matrix commonly used in the composite materials of fiber-reinforced plastics (FRP). VE resin is often combined with glass fiber in different maritime structures, such as wind turbine blades, spinner cases, and nacelle cases. However, VE resin exhibits exothermic reactions and shrinkage during curing, which often generates residual strain in large structures and those with a high stacking number. This study explored the exothermic reaction and shrinkage of VE resin and glass fiber during the vacuum-assisted resin transfer molding process, as measured using a fiber Bragg grating sensor. The experiment results verified the relationship between the stacking number and residual strain shrinkage. In addition, the symmetric laminate method was used to prevent the bending–twisting coupling effect and subsequent warping deformation of the FRP laminated plate during curing. The experiment results also verified that the bottom layers of the FRP laminated plates produced using VE resin were closer to the mold, and exhibited more shrinkage as the stacking number increased. In addition, this study discovered that during the experiment, the symmetry layer of the FRP laminated plate had a higher exothermic temperature than the bottom layer as a result of the symmetry layer’s ineffective heat dissipation. Therefore, the curing shrinkage of the symmetry layer resin was measured. The experiment results indicated that if the stacking number was between 10 and 30, the residual strain shrinkage of the symmetry layer was greater than that of the surface layer. However, because of the symmetric laminate, the residual strain of the symmetry layer did not increase when the temperature increased. Therefore, the greatest residual strain occurred at the surface of the bottom layer of the laminated plate with a stacking number of 40.