you can do so after you POP when your pes status will be
B.
Should you be posted to your unit, you must apply it through your
unit, not recruitment centre. From there your CO will fill up a
form, write a recommendation. (I was at my unit for 6 months, made
about 3-4 trips to CMPB before the recruitment centre idiots told
me that I have to apply through my unit.)
After which the airforce will decide if they want you, ask you to
go for interviews and tests. (Took them 1 year to finally send an
email to my unit)
and when they have agreed to accept you, its up to the army if they
want to release you. (For my case, army didn't want to release me.
So they sent an email to my unit asking if i mind joining after I
ORD)