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If there is no apparent advantage over using a single-source DC power source, then I think, in combination with what the other posters have described, I will go with the single-source DC power source with some kind of polarity swapping (whether it be an H-bridge or some other design). That ought to address the concern raised by FvM on the Buck Converter being Unipolar while the voltage flowing through it will be bipolar (Since the 'bipolarity' will simply come from running the current 'backwards' through the peltier, right?)

Regarding your question of the Peltier, I have it sitting on a copper plate. I do not have a dedicated heat sink for it, but I figured it would serve in a pinch.

If I can get a PID system to work, purchasing an appropriate heat sink and turning on the fan as needed to facilitate heat exchange (As needed) should be not be too complicated in terms of circuitry, right?

I am assuming it'll be connected to either the 5V pin on the Arduino, in series with a resistor to control the voltage as necessary, with the 5V being turned on /off depending on the PID. Please correct me if this is not as simple as I assume.

Thank you very much.