I assume that you have 3 drives total a standard sata ssd, a sata hdd and a msata ssd. the answer is yes so long as the caching software allows you to use the entire ssd. Intel smart response has a 64GB limit for caching so the remaining portion can be used to install other things. However you can't have the OS and the caching partition on the same SSD.
Short answer yes. Caching to a ssd would be faster then a hybrid drive. if i remember right the seagate hybrids only have 4 or 8 GB for caching. If you run a lot of different programs or games then the cache will just not be enough. Again Intel SRT allows for up to 64GB of cache.
How many and what type of drives do you have now? If you do have 3 drives (2 ssd and 1 hdd) then I would set it up like this.
Windows on the msata. Windows only need 40. Plenty of room on a 64 or 90GB. Make sure to delete hybernation files and manually set your virtual ram especially if you have 8 or more gigs of ram
All games and programs on the hdd.
Split the ssd into 2 partitions 20GBs for caching and the rest for your largest or most used games/programs.
This should give you ssd perfomance for everything you do without the need for new drives