For the public internet server, SCTP can only be used with IPv6. SCTP does not work through NAT (network address translation done by routers), so SCTP over IPv4 cannot be used. The IPv6 DNS entry for the PokerTH server is currently unavailable - this problem will be solved in the next release, from then on SCTP should work fine again.
For LAN games, you can simply use SCTP where available (e.g. on Linux). There is a very new SCTP driver for windows available here:
http://trac.sctp.jp/sctpDrv/ but I have not tested it yet, and I think it requires linking PokerTH against a specific library.