Document images are often degraded by various stains, significantly impacting their readability and hindering downstream applications such as document digitization and analysis. The absence of a comprehensive stained document dataset has limited the effectiveness of existing document enhancement methods in removing stains while preserving fine-grained details. To address this challenge, we construct StainDoc, the first large-scale, high-resolution ($2145\times2245$) dataset specifically designed for document stain removal. StainDoc comprises over 5,000 pairs of stained and clean document images across multiple scenes. This dataset encompasses a diverse range of stain types, severities, and document backgrounds, facilitating robust training and evaluation of document stain removal algorithms. Furthermore, we propose StainRestorer, a Transformer-based document stain removal approach. StainRestorer employs a memory-augmented Transformer architecture that captures hierarchical stain representations at part, instance, and semantic levels via the DocMemory module. The Stain Removal Transformer (SRTransformer) leverages these feature representations through a dual attention mechanism: an enhanced spatial attention with an expanded receptive field, and a channel attention captures channel-wise feature importance. This combination enables precise stain removal while preserving document content integrity. Extensive experiments demonstrate StainRestorer's superior performance over state-of-the-art methods on the StainDoc dataset and its variants StainDoc\_Mark and StainDoc\_Seal, establishing a new benchmark for document stain removal. Our work highlights the potential of memory-augmented Transformers for this task and contributes a valuable dataset to advance future research.