Let $M$ be simply connected smooth manifold. Prove that every real line bundle $\pi:E\to M$ is trivial.
Here is my attempt: let $\pi:E\to M$ be a line bundle. Using the fact that there is a metric $<\cdot,\cdot>$ on $E$, we can take orthonormal local sections, so that the transition functions $g_{\alpha\beta}:U_\alpha\cap U_\beta\to GL(1)$ take values on the orthogonal group $O(1)=\{1,-1\}$.
In order to prove $E$ is trivial, we need to prove that for every transition function we have $g_{\alpha\beta}\equiv 1$. I guess here is where the simply connected hypothesis comes in.
When I try to draw concrete examples, I can see that this is very intuitive, but I still can't find a way to formalize the idea that every closed path being homotopic to a point implies all transitions are the identity.
I feel like this has something to do with orientation, but I also don't know how to make this precise.
You mean real line bundle surely? Assuming, as you do, there is a reduction to structure group $O(1)$, then taking the two unit vectors in each fibre gives a two-sheeted covering map $E'\to M$. But if $M$ is simply connected then this covering is trivial: the direct product of $M$ with $\{1,-1\}$. Picking one of the sheets gives a trivialisation of $E$.