WSDL (Web Services Description Language) - this describes your service and its operations - what is the service called, which methods does it offer, what kind of in parameters and return values do these methods have?
It's a description of the behavior of the service - it's functionality.
XSD (Xml Schema Definition) - it describes the static structure of the complex data types being exchanged by those service methods. It describes the types, their fields, any restriction on those fields (like max length or a regex pattern) and so forth.
It's a description of datatypes and thus static properties of the service - it's about data.