The very early 500 (and I think 500Ds) had flat undersides to the cylinder head (the part that goes against the head gasket). Fiat later modified the heads to have a machined ring on the underside of the cylinder head and a hollow bolt, which holds the shrouding in place and is located just under the exhaust manifolds (1 per end). This hollow bolt is open to this machined ring, the theory being that if the head gasket DOES blow, the combustion fumes will exhaust out through these hollow bolts rather than be blown through the car with the 'heater air'. If your heads have this machined ring, you MUST NOT have the head skimmed to the point that the ring disappears. I would suggest that you have the head 'flash-skimmed' (i.e. just enough taken off to absolutely guarantee flatness), and then use a thin copper head gasket. These can be obtained from a number of the usual parts suppliers, but if you get stuck, I have a spare one.
As to 'porting' the head, if you would like to contact me direct, I will go through it for you.
Bigger valves---you only need to enlarge the inlet valves, but it all depends how far you want to go. To fit bigger valves, you have to fit bigger, matching valve seats--a machine shop job. If you fit bigger valves to justify that job, you either have to start playing around with carb jets or get a bigger carb, and manifold---it all starts adding up.
For a cost effective 'warm-up' I would skim the head, fit a thin copper head gasket, leave the valves standard, port the head, fit a better cam (35/75/75/35 is a good 'all-rounder'), time the cam very carefully when you fit it (with new timing gears and chain) with a timing disc, fit a better exhaust and re-jet the carb--poss up 1 size on both main and idle jets.
If you do the above to a '650' engine, you will be pleasantly surprised at the increase in performance, without leaving too big a hole in your pocket. If you are sticking with a '500' engine, you will still get an appreciable increase in performance.