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What do big international law firms (or management consultancies, etc.) pay to their expat workers in smaller countries in South America or in Eastern Europe or Subsaharan Africa? Do they pay local rates or is the pay on par with western Europe / US?

To get a job with a international law firm in a place like that, would it be better to start out the career taking internships in those developing countries or would it be better to start out in London/Paris/etc. and then transfer to a developing country?

It depends. If you go as an expat (your company in the states send you off to India), your salary will be the same, if not higher (and you'll get a cost of living allowance and business class tickets back home every year).

If you go to India and look for a job, you'll likely get a regular salary like everyone else in the office. It won't be nearly as much as you're making in the states, but it will be enough to live a similar lifestyle in India as you did in the states, if not higher because you will be a much bigger fish there.