Motivated by classical communications engineering, early works in molecular communication (MC) largely adopted established modeling and signal processing concepts from wireless electromagnetic communication systems. In the context of the human cardiovascular system (CVS), MC channel models evolved from simple unbounded and single-duct environments mimicking individual blood vessels to complex vessel network (VN) topologies, generally at the expense of analytical tractability. Up until now, this has largely prohibited rigorous communication-theoretic analysis of large-scale VNs. In this work, we leverage a recently established closed-form analytical channel model for VNs, named mixture of inverse Gaussians for hemodynamic transport (MIGHT), to conduct the first systematic communication-theoretic study of MC in complex, large-scale VNs. Based on MIGHT, we derive a Poisson channel noise model and unveil structural analogies between multipath wireless communications (MWC) and advective-diffusive MC in VNs. In particular, we establish classical MWC metrics, namely the root mean squared (RMS) delay spread, the mean excess delay, and the coherence bandwidth, for MC in VNs and derive closed-form expressions for the channel frequency response and power delay profile (PDP). Building on this characterization, we propose a VN-adapted, coherent decision-feedback (DF) detector and show how the derived multipath metrics can inform the choice of critical system parameters like the symbol duration, the sampling time, and the memory length. Additionally, we evaluate the detector's performance in different VNs exhibiting inter-symbol interference (ISI). Together, these contributions open the door to a systematic, MWC-inspired MC system design for large-scale VNs.