Try going to an external view (enable them in your difficulty settings if you need to) and making an attempt to identify the point from where the puffs originate.
I haven't spent much time in the RAF fighters except for some Hurricane sorties, but if you could tell us where the puffs of smoke appear on the airframe we might be able to give you a few more hints.
The effect you describe however is similar to a busted radiator: if you let the temps rise too much the pressure in the lines gets higher as well and it can break the pipes. When that happens, you can see white/grey puffs of steam coming out of the radiator.
Another thing which i'm not sure if its modeled in the sim is the escape valve. In the real world Spitfire there was an escape valve ahead and to the right of the windscreen, when the coolant would overheat some of it would be blown out of that valve to lessen the pressure and prevent damage to the pipes. This allowed pilots to "ride the overheat" so to speak for a small amount of time, at the expense of depleting their available coolant supply.
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