In visual localization, Absolute Pose Regression (APR) enables real-time 6-DoF camera pose inference from single images, yet critically depends on fine-tuning data quality and coverage. While recent methods leverage 3D Gaussian Splatting (3DGS) for novel view synthesis-based data augmentation, random sampling generates redundant views and noisy samples from poorly reconstructed regions. To mitigate this research gap, we propose PoseCompass, an intelligent pose selection pipeline for 3DGS-based APR. PoseCompass formulates synthetic pose selection and derives a value-based pose ranking mechanism to identify informative poses. The ranking integrates three dimensions: Localization Difficulty, favoring challenging regions; Coverage Novelty, exploring under-sampled areas; and Rendering Observability, filtering artifacts and noise. PoseCompass then generates trajectory-constrained candidates, selects the top-K ranked poses, and synthesizes views using 3DGS with lightweight diffusion-based alignment. Finally, the pose regressor is fine-tuned on mixed real and synthetic data. We evaluate PoseCompass on 7-Scenes, where it reduces adaptation time from 15.2 to 5.1 minutes, a 3x speedup, while cutting median pose errors by 53.8 percent and significantly outperforming random baselines.