The development of highly predictive analysis for designing cementitious composite with improved thermal and hygroscopic performance for building and construction poses a significant challenge. To investigate new potential applications, cement pastes have been prepared using a cement, sand, and crystallization admixture, with highly hygroscopic polymer additions (SA-PA) of sodium polyacrylate and/or recycled polyamide fibers. The porosity evolution was investigated at different curing stages and after heat treatment at 200 °C, the temperature at which the paste dehydrates quickly without structural changes. Mercury intrusion porosimetry (MIP), scanning electron microscopy (SEM), cyclic shear tests, thermal conductivity, and diffusivity measurements were carried out on the cement pastes to assess their microstructure. The behavior of the cement pastes varied with polymer additions and thermal treatments; ka−0.5 must be maximized in heat storage applications, where a and k are thermal diffusivity and conductivity, respectively. In contrast, the product a0.5k−1 must be maximized in energy-efficient insulation. Cement pastes with SA-PA exhibited the highest values of both 9.191 102 m−2 K−1 s0.5 W and 1.088 10−3 m2 K s−0.5 W−1, respectively. After the thermal treatment at 200 °C, SA-PA samples maintained the highest heat-storing performance of 6.258 102 m−2 K−1 s0.5 W, while the samples with SA-PA and polyamide fibers performed better in energy-efficient insulation, demonstrating performance of 2.552 10−3 m2 K s−0.5 W−1. These results, discussed in terms of pore size distribution, suggest potential applications in the building field and are valuable for designing plaster and concrete for applications such as thermal and hygroscopic control.