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The Kindle for PC app is tied to the country from which you downloaded it, and you can only register it your account in that country. So, if you download it from Amazon.co.uk, you must register it to an account with Amazon.co..uk, and ditto with Amazon.com.
By the way, this is not at all obvious from the program itself. There's nothing in the user interface that tells you which country the app belongs to (as far as I know).
Now, once you have registered with a given country, you can purchase books from that country's Kindle store. But - not if there are territorial restrictions on the book in question. If the book isn't available for your country, you can't purchase it, regardless of whether you're using the app or a physical device.
For any given book, you can discover if there are restrictions by going to the book's page on the Amazon website (after logging into your account). If you see a note saying that pricing information is not available, then the book cannot be bought by purchasers in your country.
Buying a physical Kindle from the UK wouldn't help, even if you could. Unlike with the Kindle for PC software, the Kindle is not tied to any particular country. You could buy one in the US, and still register it to the Kindle UK store. But you'd still be up against the same geographic restrictions.
If the territorial restrictions don't apply to the book you want to buy, you could purchase it through the PC program, as per the above. But, remember, each copy is branded for a particular device, so you wouldn't be able to simply copy it to the physical Kindle (at least, now without making certain changes to it, which I understand we're not supposed to talk about here).
Please note that I am not an expert in this area. The above is based entirely on my personal experience as a "dual nationality" (UK and USA) Kindle user.
Mike
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