The retrogradation of starch strongly influences the texture and stability of starchy foods. This study applied low-field nuclear magnetic resonance (LF NMR) to examine the effect of buckwheat hull (BH) fiber and green barley (GB) on water dynamics in normal (NPS) and waxy (WPS) potato starch gels. Relaxation times (T1, T2) and mean correlation times (τc) were monitored during 15 days of storage to evaluate changes in water mobility and starch–polymer interactions. Results showed that WPS, with its high amylopectin content, retrograded earlier than NPS. The addition of BH inhibited conformational changes associated with water binding in WPS gels, indicating that insoluble fiber entrapped water within the amylopectin network. Conversely, GB promoted higher τc values in WPS, reflecting enhanced ordering and reduced water mobility, while its impact on NPS was minor. In NPS systems, BH decreased τc, suggesting disruption of amylose-driven structural reorganization. These findings demonstrate that BH and GB exert opposite effects on starch retrogradation and highlight their potential as functional additives for tailoring texture and stability in starch-based food systems.