If your xml document does not have a reference to the xml schema, you should add it yourself, then validate with NSXMLDocument validateAndReturnError:
method.
Here is an example of how to tweak the xml document to have a reference to the xsd. Obviously, you will have to adapt this code to have a reference to your local xsd file.
NSError *error = nil;
NSURL *xmlURL = [NSURL URLWithString:@"http://www.xmlschema.info/PO.xml"];
NSXMLDocument *document = [[NSXMLDocument alloc] initWithContentsOfURL:xmlURL options:NSXMLNodeOptionsNone error:NULL];
NSXMLNode *noNamespaceSchemaLocation = [NSXMLNode attributeWithName:@"xsi:noNamespaceSchemaLocation" stringValue:@"http://www.xmlschema.info/PO.xsd"];
NSXMLElement *rootElement = [document rootElement];
NSMutableArray *rootAttributes = [[rootElement attributes] mutableCopy];
[rootAttributes replaceObjectAtIndex:1 withObject:noNamespaceSchemaLocation];
[rootElement setAttributes:rootAttributes];
BOOL isValid = [document validateAndReturnError:&error];
if (isValid)
NSLog(@"document is valid");
else
NSLog(@"document is invalid: %@", [error localizedDescription]);