The first port of call for
child maintenance is the natural parent, but when a
step parent has accepted the child as family and assumed responsibility
for maintaining the child they could be called upon by the courts to
maintain the child if the natural parent hadn't been supporting the child
eg if the natural parent had died or disappeared.
Court orders
are for child maintenance payments are made to the child or the parent with
the majority of care for the benefit of the child. There is no provision as
far as I'm aware for step parents to be ordered to pay maintenance to the
non resident parent.
In any case how old are the children?
Usually the CSA, not the courts, has jurisdiction over
child support for under 18s in full time education.
Only if the natural parent had died or couldn't be traced would the courts
have the authority to make an order for child maintenance from a step
parent.