In this paper, single pulse (SP)- and double pulse (DP)- Laser Induced Breakdown Spectroscopy (LIBS) on metallic titanium, aluminum-based alloy and copper-based alloy have been studied by spectrally resolved imaging to find out the fundamental difference in terms of fluid-dynamic and chemical aspects. To better clarify the different nature of SP- and DP-Laser Induced Plasma (LIP) a qualitative theoretical model including both fluid-dynamics and chemical processes has been applied for the interpretation of the experimental results. Moreover, an attempt to quantify the mechanisms inducing the DP-LIBS enhancement has been made. By the analysis of spectrally resolved imaging data, the temporal and spatial maps of the emission signal and of the corresponding DP-LIBS enhancement have been built in order to improve the analytical information conveyed. Finally, it has been pointed out the important effect of the different environment where SP- and DP-LIPs expand, as well as its relevance to the understanding of the basic questions underlying the comparison between SP- and DP-LIBS.