Over the recent years, reinforcement learning (RL) starts to show promising results in tackling combinatorial optimization (CO) problems, in particular when coupled with curriculum learning to facilitate training. Despite emerging empirical evidence, theoretical study on why RL helps is still at its early stage. This paper presents the first systematic study on policy optimization methods for online CO problems. We show that online CO problems can be naturally formulated as latent Markov Decision Processes (LMDPs), and prove convergence bounds on natural policy gradient (NPG) for solving LMDPs. Furthermore, our theory explains the benefit of curriculum learning: it can find a strong sampling policy and reduce the distribution shift, a critical quantity that governs the convergence rate in our theorem. For a canonical online CO problem, Secretary Problem, we formally prove that distribution shift is reduced exponentially with curriculum learning even if the curriculum is randomly generated. Our theory also shows we can simplify the curriculum learning scheme used in prior work from multi-step to single-step. Lastly, we provide extensive experiments on Secretary Problem and Online Knapsack to verify our findings.