...I'll have another trawl of the 'net tomorrow

& see if I can dig a bit deeper into what's going on.
Wow, it's been a fascinating bit of homework.
I've found this article, which neatly brings together my posts, Maxi's posts, nextgreencar.com and the press launch articles and appears to solve the mystery:
http://autoinsight.blogosfere.it/2007/07/nuova-fiat-500-una-euro-5-omologata-euro-4-ecco-perche.html
It's written in Italian; someone with better knowledge of the language than I might be able to extract more of the nuances from it, but online translation offers the following*:
A po' reigns; of confusion between the motorists. They ask to me: but Fiat, with the 500 (all the post they regard that it), than strategy has adopted here with regard to the polluting emissions? Then, I try to make a po' d' order. The Cinquino respects the norms antipollution Euro 5. It wants to say that it is ahead in the time. Thus they have made other Houses all' vanguard, like l' Audios with some models. However, the 500 come accredited like Euro 4. Sul booklet you will find written Euro 4. The reason is simple: the norms Euro 5 still have not entered in vigor. To this point, it would be pretty if Fiat - once arrived the law dell' Euro 5 - it made pressure on the Department of the terrestrial transports (l' former Motorization, in order to mean to us) so that the passage concurred, on the papers of circulation of the 500, from Euro 4 to Euro 5. It would be enough brand adhesive to apply on the booklet. Goodness knows Fiat that thinks some. That dicitura 5 Euros a day could serve in order to pay a stamp less beloved, for circular in days of block of the traffic, in order to maintain a value trades them high.
*
This isn't the clearest translation I found, but it is the funniest 
.
The way I'm interpreting this, is that FIAT designed the 500 from the outset to exceed Euro5 emission limits, but only
certified the cars to Euro4 standard at launch. All the cars were re-certified to Euro5 for the 2010 model year. So, pre-2010 cars have CO, HC & NOx emissions which meet Euro5 standards, but only have Euro4 certification.
This might have implications in the future for owners & purchasers of secondhand cars if Euro5
certification (as opposed to compliance with Euro5 limits) is needed in order to comply with local legislation or secure a fiscal advantage.
nextgreencar.com gives different CO, HC & NOx numbers for pre and post 2010 500s (models with & without S/S are listed separately in both categories). This may be because some small change was needed to get the Euro5 stamp, or it may just be a quirk of the recertification process.
The emissions numbers on my V5C correspond exactly to those given on nextgreencar.com for a 2010 S/S 1.2, which does give some credence to that website.