Absolutely, that's a given.
Keep the can well shaken and upright and, as you say, give it some primer blasts before you move in for the kill, and make sure you don't get too close with the nozzle and linger too long on one spot, though, and there is no substitute. For years we used those to clean out the insides of PCs in client offices; these were PCs that were loaded with everything from memory cache boards to network I/O cards that had filled up their ISA/EISA/PCI (depending upon the age of the PC) slots to the maximum, and the only efficient way of cleaning off the boards without taking each of them out individually and painiting them was to give them a good blast of compressed air. With literally hundreds of PCs - servers and clients - and thousands of boards over several years, we never had a single issue with one of these PCs that was even closely related to compressed air condensation.
Used right, compressed air condensation is not a problem, and sometimes
 there is no legitimate practical substitute. And it's far better on electronics to take the blanket of dust off than it is to levae it on. Those expansion boards were a good example. An even better one in my own studio is the amps on my HR824s. Without taking the amps apart, there is no good way to get at the dust that filters throuh the vents in the back and onto the heat sinks. I've been regularly blasting compressed air through there to keep the sinks somewhat dusted. Both this method and my monitors have worked great for me for going on 8 years and counting.
All that siad, though, I'd still reserve the compressed air only for those areas or surfaces not effectively or readily accessable by a vacuum or brush. Not only for the potential condensation reasons previously given, but for an even better reason; the shit's just too damn expensive! 

  That crap makes the rip-off otherwise known as bottled water look like a downright bargain 

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G.