Measurements of the $^2$H($^{16}$C,$^{16}$C$^{*}$$\rightarrow^4$He+$^{12}$Be or $^6$He+$^{10}$Be)$^2$H inelastic excitation and cluster-decay reactions have been carried out at a beam energy of about 23.5 MeV/u. A specially designed detection system, including one multi-layer silicon-strip telescope at around zero degrees, has allowed the high-efficiency three-fold coincident detection and therefore the event-by-event determination of the energy of the unstable nucleus beam. The decay paths from the $^{16}$C resonances to various states of the final $^{10}$Be or $^{12}$Be nucleus are recognized thanks to the well-resolved $Q$-value spectra. The reconstructed resonances at 16.5(1), 17.3(2), 19.4(1) and 21.6(2) MeV are assigned as the $0^+$, $2^+$, $4^+$ and $6^+$ members, respectively, of the positive-parity $(3/2_\pi^-)^2(1/2_\sigma^-)^2$-bond linear-chain molecular band in $^{16}$C, based on the angular correlation analysis for the 16.5 MeV state and the excellent agreement of decay patterns between the measurements and theoretical predictions. Moreover, another intriguing high-lying state was observed at 27.2(1) MeV which decays almost exclusively to the $\sim$6 MeV states of $^{10}$Be, in line with the newly predicted pure $\sigma$-bond linear-chain configuration.