Algorithm for determining if there is exactly one Eulerian path
Do you know an algorithm for finding Eulerian paths?
Fleury's algorithm begins at one of the endpoints and draws out the eulerian path one edge at a time, then imagine removing that edge from the graph. The only trick to the algorithm is that it never chooses an edge that will disconnect the graph. Only with that condition, it is guaranteed to never get stuck in tracing out an eulerian path.
So, as long as that choice of edge is unique at every step, the eulerian path will be unique. If ever there are two choices that can be made which are valid (i.e. they each would not disconnect the graph) then you have multiple eulerian paths.