Marine plastispheres represent dynamic microhabitats where microorganisms colonise plastic debris and interact. Metaproteomics has provided novel insights into the metabolic processes within these communities, however the early metabolic interactions driving the plastisphere formation remain unclear. This study utilised metaproteomic and metagenomic approaches to explore early plastisphere formation on low-density polyethylene (LDPE) over three (D3) and seven (D7) days, focusing on microbial diversity, metabolic activity, and biofilm development. In total, 2,948 proteins were analysed, revealing dominant proteomes from Pseudomonas and Marinomonas, with near-complete metagenome-assembled genomes. Pseudomonas dominated at D3, while at D7, Marinomonas, along with Acinetobacter, Vibrio, and other genera became more prevalent. Pseudomonas and Marinomonas showed high expression of reactive oxygen species (ROS) suppression proteins, associated with oxidative stress regulation, while granule formation, and alternative carbon utilisation enzymes, also indicated nutrient limitations. Interestingly, 13 alkane and other xenobiotic degradation enzymes were expressed by five genera. The expression of toxins, several type VI secretion system (TVISS) proteins, and biofilm formation proteins by Pseudomonas indicated their competitive advantage against other taxa. Upregulated metabolic pathways, including those relating to substrate transport also suggested enhanced nutrient cross-feeding within the biofilm. These insights enhance our understanding of plastisphere ecology and its potential for biotechnological applications.