Diffusion models have demonstrated remarkable success in image and video generation, yet their practical deployment remains hindered by the substantial computational overhead of multi-step iterative sampling. Among acceleration strategies, caching-based methods offer a training-free and effective solution by reusing or predicting features across timesteps. However, existing approaches rely on fixed or locally adaptive schedules without considering the global structure of the denoising trajectory, often leading to error accumulation and visual artifacts. To overcome this limitation, we propose DPCache, a novel training-free acceleration framework that formulates diffusion sampling acceleration as a global path planning problem. DPCache constructs a Path-Aware Cost Tensor from a small calibration set to quantify the path-dependent error of skipping timesteps conditioned on the preceding key timestep. Leveraging this tensor, DPCache employs dynamic programming to select an optimal sequence of key timesteps that minimizes the total path cost while preserving trajectory fidelity. During inference, the model performs full computations only at these key timesteps, while intermediate outputs are efficiently predicted using cached features. Extensive experiments on DiT, FLUX, and HunyuanVideo demonstrate that DPCache achieves strong acceleration with minimal quality loss, outperforming prior acceleration methods by $+$0.031 ImageReward at 4.87$\times$ speedup and even surpassing the full-step baseline by $+$0.028 ImageReward at 3.54$\times$ speedup on FLUX, validating the effectiveness of our path-aware global scheduling framework. Code will be released at https://github.com/argsss/DPCache.