If you need to do a file upload, you'll need to use MediaType.MULTIPART_FORM_DATA_TYPE. Looks like MultivaluedMap cannot be used with that so here's a solution with FormDataMultiPart.
InputStream stream = getClass().getClassLoader().getResourceAsStream(fileNameToUpload);
FormDataMultiPart part = new FormDataMultiPart();
part.field("String_key", "String_value");
part.field("fileToUpload", stream, MediaType.TEXT_PLAIN_TYPE);
String response = WebResource.type(MediaType.MULTIPART_FORM_DATA_TYPE).post(String.class, part);