If you compare libs/ vs. Lib/ you'll notice that the latter is full of *.py files and the former has *.lib files. Further investigation with a text editor will show that *.py files are human-readable (I hope) and the *.lib files are not.
And that's really the difference. If you want to know more, the .lib files are static-link libraries, used for building .dlls, C extensions, and all that good stuff. Head on down the rabbit hole if that interests you.
On to the meat of your question: are you supposed to be able to drop modules in there and be able to import them? Not really. That is a side effect of that folder being included in your path. From the Modules docs:
When a module named spam is imported, the interpreter first searches for a built-in module with that name. If not found, it then searches for a file named spam.py in a list of directories given by the variable sys.path. sys.path is initialized from these locations:
- the directory containing the input script (or the current directory).
- PYTHONPATH (a list of directory names, with the same syntax as the shell variable PATH).
- the installation-dependent default.
Various installation methods will modify %PATH% or %PYTHONPATH% so I can't tell you exactly where to look; on my windows box, the python installer modified %PATH% for me, so you should probably look there first. Notably, my path does not include Python33/libs/ so I would not expect it to be there by default.