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Are you sure that such a program - to choose email client? - exists? It's normal only to install a single email client on a machine, if one installs one at all - many people these days just use a webmail service.
OSes generally allow one to set which program to use (ie the default one) when browsing things, and if you want, which program for email and news (ie NNTP / Usenet). But that's just telling the OS that you do have a specific program you want to use to process any email or http[s] links you find in other apps, so that if for example you click on a URL somewhere it will immediately pass that to the program you want to process it.
Often the way you tell the OS that such-and-such a client is to be considered the default email/ news/ browser is via that program's own Settings/Preferences. Some will also re-check that they are still set as default every time that they are started.
I do not see why a choice of email program would make it easier to send to multiple parties. I'd expect any email program to be able to do that.
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