Assuming table c has the currently configured value and table d contains the system defaults
both with fields key (unique constraint) and val
I can use a union query to look up values
select top 1 * from (
select 'c' source, key, val from c
union all
select 'd', key, val from d
) x
where key = 'something'
order by source
this will return the configured value if it exists or the default if it does not. I kind of agree with @bohemian - not sure I see the point of the insert, if the default value is changed then the query will still work.
If you really want to do the insert maybe look at rolling out a stored proc.