It is pretty much clear from the name itself. Append means attaching something to the last of a list whereas extend means growing the existing list, Obviously from the last. In both the cases something new is added to the last of the list, but the difference will be more clearer from the example.
first_list = [10,30]
second_list = [100,101]
first_list.append([40,50])
second_list.extend([102,103])
print first_list
[10, 30, [40, 50]]
print second_list
[ 100, 101, 102, 103]