Guayadeque's .desktop file has a bug, so it isn't possible to use it to open files for playing from your file manager (there is no way for the file manager to pass along to Guayadeque which file it is to play). Guayadeque does support this though, so you can fix that. Somebody should probably also report this as a bug to either the Ubuntu or Debian maintainers of the package, so it can be fixed permanently.
The file /usr/share/applications/guayadeque.desktop describes how the program can be started, which on the 0.3.5 version I installed from the Ubuntu repository has the following line for that:
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Exec=guayadeque
You need to edit the /usr/share/applications/guayadeque.desktop file, which you can do with:
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gksudo gedit /usr/share/applications/guayadeque.desktop
And then change the above line to the following, so that the program can also be used to open files:
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Exec=guayadeque %U
On recent version of Cinnamon, one where you have Nemo as the file manager, you will then also be able to right-click a music file in your file manager, go to Properties from the context menu and on the Open With tab there set Guayadeque as the default. You need Linux Mint 13 with backports (
http://blog.linuxmint.com/?p=2225) or Linux Mint 14 for this to work ; I'm not sure you can do this on Linux Mint 12 as that still has Nautilus as a file manager and that has reduced functionality. You will want a newer version of Cinnamon anyway, to get the awesome sound applet integration

(See for examples of what newer Cinnamon version brings:
http://cinnamon.linuxmint.com/?p=207.)
BTW, I hope you are aware that Linux Mint 12 reaches end of life next month. Recommend you start considering what version of Linux Mint you want to install. Linux Mint 15 is approaching on the horizon, so you might just wait for that. A newer version of Linux Mint will give you a much better Cinnamon experience as well.