Clever -- ordering Radio Times originally (6)
I believe the answer is:
adroit
'clever' is the definition.
(synonyms)
'ordering radio times originally' is the wordplay.
'ordering' indicates an anagram.
'originally' suggests taking the first letters.
The initial letter of 'times' is 't'.
'radio' is an anagram of 'adroi'.
'adroi'+'t'='ADROIT'
(Other definitions for adroit that I've seen before include "Clever, skilful" , "Quick and clever in action or thought" , "Skilled" , "Quick or adept" , "Deft and proficient" .)