would help if you told us exactly what model pioneer HU.
the YELLOW wire on the pioneer (and virtually all aftermarket HUs) is the main powerwire to supply juice to the unit to function. plus it provides memory backup for all settings/radio. so it must be connected to the main 'constant' +12V powerwire in the plug, which is wire #7 in the alfa plug.
the RED wire on the pioneer is 'meant' to be for a 'switched'/ACC +12V powerwire. one that is 0V with key at OFF, and +12V with key at ACC/ON. of course, fiat's/alfa's do not have such a wire in the plug. as such, most people also connect this to the main powerwire, #7. this means the HU does not turn off when you turn the key to OFF. this wire does NOT provide memory or supply the main power to the unit. it is merely an 'electrical trigger' to turn the HU on/off.
it is the RED wire you can put a manual switch along if you wish, which is a good idea. extend the wires and position the switch in a convenient position somewhere under the dash or wherever.
note, there may be a suitable 'switched' powerwire you could tap into for the RED wire, like the cigarette lighter powerwire. use a multimeter to confirm the wire is appropriate (an essential tool for any such electrical work).
as mentioned, you will require an SWI (steering wheel interface) to connect between the alfa mini-ISO green plug and the pioneer, which converts 'alfa signals' into 'pioneer signals'. surprised the retailer did not explain this to you (though you may be buying online which would explain a lack of service!

).
