For primitives, there is no difference between using initializer lists or constructing them via assignment.
For other types, initializer lists might afford you performance improvements when constructing objects.
Do note that the order of initializing (in initializer lists) depends on the order of declaration in the class. If the declarations are out of order and you need to construct data that depends on something else already being initialized before hand, that is an exception to the 'use initialization lists when possible rule'.
More info: http://www.parashift.com/c++-faq-lite/ctors.html#faq-10.6