When shield tunneling is performed in water-rich silt and fine sand strata, the grout becomes runny when diluted by groundwater. After dilution, the filling effect of the grout is not significant, and the level of surface settlement is very high. In this study, based on bidding section 04 of Tianjin Metro Line 11, traditional grouting materials were selected to conduct response surface method (RSM) tests. The purposes of the RSM analysis were to analyze the interactions between materials and their influences on grout performance and to optimize the grout mix ratio. Various admixtures were compared to assess the effects of different admixtures and compositions on the dispersion resistance and flow performance of the grout. Finally, a shield synchronous grouting test system was developed, and a similar indoor grouting simulation test was performed to analyze the influences of the different admixtures on the filling effects and to determine a reasonable grout mix ratio. The following three results were obtained. (1) The RSM was suitable for grout performance prediction and grout mix ratio optimization, and hydroxyethyl cellulose could improve the grout performance and increase the bond performance between the cementing material and aggregate. (2) Admixture incorporation enhancement could improve the grout utilization rate and increase the diffusion distance at the top of the tunnel, which would be conducive to filling the gap at the tail end of the shield. (3) The optimal preparation scheme of grout in water-rich fine sand formations included a water–binder ratio of 0.72, cement–sand ratio of 0.80, fly ash content of 5%, bentonite content of 14.94%, and admixture content of 0.8%–0.9%