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You can use the DateTime.format(String) method and a Java SimpleDateFormat as the parameter.

System.debug(Datetime.now().format('yyyy-MM-dd\'T\'HH:mm:ss.SSSZ'));

gives:

2015-05-12T15:43:36.358-0700

This will be for the current users local time zone. Note:

"If the time zone cannot be determined, GMT is used."

If you want more control over the timezone you can use the DateTime.format(String, String) method and specify the TimeZone.