If there is exactly one directed path between every pair of nodes, then
- every node must have at least one out-edge (else no paths from that node to other nodes)
- no node can have have more than one out-edge (if there is an edge from X to Y and an edge from X to Z, and there are paths from Y to T and from Z to T, then there are multiple paths from X to T)
But now, with every node having exactly one out-edge, and every node being reachable from every other node, the graph must be a single directed cycle.
That is trivial to check in O(n) time.
Edit: As Erik P notes in the comments, this argument only applies if the paths in question are simple paths. In the same spirit, a graph of size 3 may need special treatment, because the X-Y-Z-T reasoning above doesn't apply, which means a graph with nodes X,Y,Z and edges from X to Y and Z, and from Y and Z to X would be legal.