Maximum PC

First & foremost, are there any amazing media players that make Apple's vanilla one look bad?

And, any other apps you think I should look into, preferably free at the moment.

Kindle App is a must is your enjoy reading. You can look into emotobooks, they are pretty sweet. Just google it.
I would get a few games so you're not bored. If you like RPG's/MMO's I'd try "World of Magic" Prolly one of the best free ones out there, but a lot of exp grinding.
I don't use my iTouch that much except for just music these days since I use my smart phone for everything now. But I still have all the basic app's on my touch. Like, Twitter, Facebook, Google+, Paypal, Etc Etc

simply google it or go to apple store.. you will find many.

Would really love to help you find free applications for your iPod touch, but I'm not sure if it is allowed to post the links here. One way you can do so (which is really easy in fact) is what ndkpromotions said - Google it. If you don't want to risk your Touch getting haywired or compromise then it would be best to check out Apple store. There are free applications there which though not really cool, might help improve your iTouch experience.

With that said, i also prefer to use the iPhone these days as it is easy to carry one than several devices which can be bothersome and might not fit my small purse