I'd say get Resistance 2 first, because online shooters generally worsen over time as the game becomes older and people move on to other games. It's most enjoyable when many people are active online.
Also, LittleBigPlanet, with its user-created content, will only improve over time, and with the current ridiculous copyright issues, I'd say save this for last - wait until they've sorted out those pesky restrictions on uploading levels.
Valkyria Chronicles gets the middle spot by default, but that doesn't mean that it's not a great game because it certainly is.
It's worth noting that if you're not into playing shooters online, and if you don't have a buddy to play through the co-op campaign with, I'd consider a rental for Resistance 2. Also, LittleBigPlanet is definitely not worth $60 without the online aspect, so don't even bother with it if you can't play online.
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