As @fpmurphy said, the compiler flags are not usually preserved within the binary. And the build-time options like --multipath=X are most likely options for the ./configure script, so they might do something like controlling the generation of a config.h file, which will then participate in the build process without necessarily affecting compiler flags at all.
But when a program has a lot of such options, there is sometimes (not always) a way to find out the state of the relevant build-time options. If this information is available, it can often displayed via programname --version or similar option that displays version information.
I don't know Quagga at all, but the documentation section describing its Terminal Mode Commands has one promising-looking command:
Command: show version
Show the current version of Quagga and its build host information.
The "build host information" just might include information about the build-time options. Or it might not. But if I had no easier sources of information, that would be one of the first places I'd look.
If the software is packaged, and you can find the corresponding source package, the general idea is that the source package includes all the build-time configuration required to produce a binary that is at least 100% functionally equivalent to the one distributed in the corresponding binary package(s) of the same distribution. If the distribution is using the new-ish "reproducible builds" techniques, the resulting binary might even be bit-for-bit identical.
So, the source package (and in the case of a RPM, its .spec file in particular) is a good source of information on build-time options used in the corresponding binary package.
Assuming that the source RPM whose .spec file you checked also came from CentOS's repository and had the same version as your binary, the standard assumption would be that yes, --multipath=64 was used in producing the binary RPM. If you find that's not actually true, that would be a very good reason to make a bug report or otherwise contact the distributor and report the discrepancy.