you are right. all you need to do is to create a simple web service in PHP, which accepts the request/xml/file and then stores it in a database. then you can use the webservice using any technology, C# for sure.
in order to write a web service in PHP, I think it is better to choose your webservice type in the first step. it can be a REST web service, or SOAP, or XML-RPC. it depends on the level of complexity of your application.
if your application is as simple as just throwing a string to the webservice or a file URL, so then the webservice can store that string, or fetch the file from the URL and stores it in database, I recomment REST. because it is simpler. as simple as just writing a simple PHP script that uses it's HTTP parameters as input.
but incase you want it to be more secure or have more complex needs, It is easy to have SOAP services in PHP. if you wanted to work with SOAP, PHP has an extension (php-soap) which you can install and use the built-in functionality of PHP-SOAP. if you are using an older version of PHP that does not support the extension, or your application will be hosted where php-soap is not installed, there is pure PHP implementaion of SOAP protocol, named nusoap. it is open source and works very well.
http://sourceforge.net/projects/nusoap/