I was having problems here (i.e. sending form-data whilst uploading a file) until I used the following:
files = {'file': (filename, open(filepath, 'rb'), 'text/xml'),
'Content-Disposition': 'form-data; name="file"; filename="' + filename + '"',
'Content-Type': 'text/xml'}
That's the input that ended up working for me. In Chrome Dev Tools -> Network tab, I clicked the request I was interested in. In the Headers tab, there's a Form Data section, and it showed both the Content-Disposition and the Content-Type headers being set there.
I did NOT need to set headers in the actual requests.post() command for this to succeed (including them actually caused it to fail)