Make a complete graph of 4 vertices. Assign weight=1 to three edges and weight=2 to 4th edge and both diagonals.
Now weight of minimum spanning tree= 3. It's unique here.
Weight of second best spanning tree=4. But its not unique in this graph. 4 such spanning trees are possible.
Now another example where weights are distinct. A graph like above but with one diagonal. Let 4 edges have weights 1,2,3,5 and weight of diagonal is 4.
MST will consist of (1,2,3).
Two second best MSTs will be (1,2,5) and (1,3,4). So again, second best MST is not unique.