That stereo will get you started, but it's not going to do everything you want. Or think you want.
1st. If you do not have front speakers, you really should start there. If you are going to run 2 speakers off the head unit, and 2 speakers off an amplifier, then the amplifier should be powering the front speakers.
My answer is going to assume you have front speakers, or front and rear speakers running off the head unit. (the pioneer).
That stereo has a HPF/LPF, and so setting it to low pass filter will give you a subwoofer control option. This is a good thing. I would only do a subwoofer and amplifier off of that stereo, otherwise you would not be able to control the subwoofer volume separately. If you want to have an amplifier on 2 speakers and a subwoofer (3 channel or 4 channel amplifier with channels 3/4 bridged into mono) then that would work as well, but unless the amplifier has a remote control for sub volume, the percentages will be fixed.
so to answer your question: yes, it will work, but with very limited adjustments. A newer stereo with at least 2 preouts would be a preferred.