Try:
String value = nlLastFm.item(0).getTextContent()
A little test code(with smaller piece of your xml and xpath edited accordingly)
public static void main(String[] args) throws ParserConfigurationException,
SAXException, IOException, XPathExpressionException {
String xml = "<album position=\"1\"><artist>Cher</artist><title>Believe</title><mbid>61bf0388-b8a9-48f4-81d1-7eb02706dfb0</mbid><url>http://www.last.fm/music/Cher/Believe</url><image size=\"small\">http://userserve-ak.last.fm/serve/34/8674593.jpg</image><image size=\"medium\">http://userserve-ak.last.fm/serve/64/8674593.jpg</image><image size=\"large\">http://userserve-ak.last.fm/serve/126/8674593.jpg</image></album>";
InputStream stream = new ByteArrayInputStream(xml.getBytes("UTF-8"));
DocumentBuilderFactory factory = DocumentBuilderFactory.newInstance();
DocumentBuilder builder = factory.newDocumentBuilder();
Document documento = builder.parse(stream);
XPathFactory xPathfactory = XPathFactory.newInstance();
XPath xpath = xPathfactory.newXPath();
XPathExpression expr = xpath.compile("//album/image[@size='medium']");
NodeList nlLastFm = (NodeList) expr.evaluate(documento,
XPathConstants.NODESET);
String coverUrl = nlLastFm.item(0).getTextContent();
System.out.println(coverUrl);
}