Rich lady orders another double espresso decaf to begin with (6)
I believe the answer is:
loaded
'rich' is the definition.
(similar in meaning)
'lady orders another double espresso decaf to begin with' is the wordplay.
'to begin with' indicates taking the first letters.
The initial letters of 'lady orders another double espresso decaf' is 'LOADED'.
(Other definitions for loaded that I've seen before include "Rolling" , "Big Bertha sometimes was" , "Rich - drunk - with a heavy burden" , "Slangily very rich - or burdened." , "drunk- > biased" .)