seeing as the tools part has been covered, here is something for the techniques.
Depending what it is you need to hook and whether or not there is protection invloved, there are a few methods:
Relative call/jmp patching in the virtualized binary: this is the simplest, but also a lot of work if you can't automatically find all references to a function, this probably won't work in this cause due to your criteria.
IAT/EAT hooking: this is use for imports(IAT) and exports(EAT), great if your targeting a known importted/exported set of API functions. a good example of this can be found here or here
Hot-Patching: Windows XP SP2 introduced something called "hot-patching" (used for realtime system function updates), where all its (the WinAPI) functions start with a 'mov edi,edi', allowing a relative jump to be patched into the free space created above every hot-patchable function(one can do it too). this is generally used for programs that checksum there IAT's or have other funny forms of protection, more info can be found here and here
Code-Caving: capturing execution flow by placing redirections in arbitrary code space. see here, here or here
VFT/COM Redirection: basically overwriting entries in a objects virtual function table, useful for OOP/COM based applications. see this
There are a lot of 3rd party libraries, most famous would probably be MS Detours, one can also look at APIHijack or a mini-hook engine.
Ofcourse nothing can substitute for the initial poking you'll need to do with a debugger like ollydbg, but knowing the method your gonna use can drastically short them amount time time spent poking around