You would need some sort of switching converter for that, they are available as monolythic circuits CPC stock them, as would many other supplyers I am sure.
(Asuming you dont want to try and build one.)
Are you stuck with those rails?
where is your 5v / 3.3v coming from?
Have a look at :- http://cpc.farnell.com/jsp/level5/module.jsp?moduleId=cpc/506853.xml
The output is isolated so you can configure tham however you want to just treat them as if they were batteries .. connecting the positive output to your ground will mean thet the negative output is now a -V rail.
you would only need 1 and your existing 5V.
Just one simple way ... there are probably loads of other solutions.