string.append is much faster. Especially when you reserve.
If you are concatenating only strings, I would use string.append. I would only use stringstream when I need to automatically convert non-strings to strings for example:
const int x(42);
stringstream ss;
ss << "My favorite number is: " << x << std::endl;
Here stringstream automatically converts x to a string and appends it. I do not need to call atoi. Stringstream will convert all the basic types automatically for you. It is great for that purpose.
Also if you are only going to be directing data into the stringstream to convert it to a string later. You can use ostringstream which is for output.
I hope that helps.