The recent past has witnessed a notable surge in on-demand food delivery (OFD) services, offering delivery fulfillment within dozens of minutes after an order is placed. In OFD, pooling multiple orders for simultaneous delivery in real-time order assignment is a pivotal efficiency source, which may in turn extend delivery time. Constructing high-quality order pooling to harmonize platform efficiency with the experiences of consumers and couriers, is crucial to OFD platforms. However, the complexity and real-time nature of order assignment, making extensive calculations impractical, significantly limit the potential for order consolidation. Moreover, offline environment is frequently riddled with unknown factors, posing challenges for the platform's perceptibility and pooling decisions. Nevertheless, delivery behaviors of skilled couriers (SCs) who know the environment well, can improve system awareness and effectively inform decisions. Hence a SC delivery network (SCDN) is constructed, based on an enhanced attributed heterogeneous network embedding approach tailored for OFD. It aims to extract features from rich temporal and spatial information, and uncover the latent potential for order combinations embedded within SC trajectories. Accordingly, the vast search space of order assignment can be effectively pruned through scalable similarity calculations of low-dimensional vectors, making comprehensive and high-quality pooling outcomes more easily identified in real time. SCDN has now been deployed in Meituan dispatch system. Online tests reveal that with SCDN, the pooling quality and extent have been greatly improved. And our system can boost couriers'efficiency by 45-55% during noon peak hours, while upholding the timely delivery commitment.