One of the on'yomi readings of 相 is しょう. If I'm doing my legwork right, when it's read this way, it has an indication of government involvement, in words like (and here, I'm relying on my dictionaries—I have no idea if these words are commonly used?)

丞相 じょうしょう "emperor's assistant"
首相 しゅしょう "prime minister" ← I thought the word for this was 総理大臣 そうりだいじん?

Apart from my prime minister question above, I'm struggling to understand what is really meant by "government minister". Is this a government minister of old? (China, even?) Is this contemporarily used for ministers in the government? What level of minister are we talking about? Any old minister, or is it for special ones?

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    首相 is still a reasonably common word; it's just that the 首相 of Japan is more properly known as the 内閣総理大臣. – Zhen Lin Jan 30 '14 at 19:20

[相]{しょう} = [大臣]{だいじん}

It refers to the head of each [省]{しょう}(Ministry) of the Japanese Government. The U.S. counterpart of our 省 would be "Department". 大臣 is the "official" word and 相 is used like a nickname as 大臣 looks and sounds pretty heavy for everyday use.

To take [文部科学省]{もんぶかがくしょう}(Ministry of Education, Culture, Sports, Science and Technology) as an example, its head is officially named [文部科学大臣]{もんぶかがくだいじん} but since that is long, it is very often shortened to [文科相]{もんかしょう}.

As for the Prime Minister, you will see/hear (therefore need to know) all of [内閣総理大臣]{ないかくそうりだいじん}、[総理大臣]{そうりだいじん}、[首相]{しゅしょう} and [総理]{そうり} in the order of formality.  総理, with or without a family name in front, would be like "Mr. President" in the U.S.

Finally, unless you are planning to be like Donald Keene, you do not need to know the word 丞相. It has much more to do with old China than old or current Japan. 

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