Ok, first off, a big thanks to everyone who has made a contribution thus far. Rather than reply to everyone individually, I shall post an update, as I've been tinkering tonight.
I picked up some Akasa 450 Thermal Paste on the way back from work, and have spent this evening taking my pc apart. I've put the new paste on, and attached the HSF with the mobo out of the case. Initial results were positive, as my BIOS was reporting CPU temp around 5c lower than before.
I'm currently running the E4400 at 3ghz (last night most of my testing was done at 2.66), 1.325v and smartfan disabled. Coretemp 0.95.4 is showing idle temps of around 42c, with TAT around 5c higher. I'm finding it difficult to get accurate temps as they keep going up and down regularly on both programs whether the system is idling or under load. Running a blend test on orthos for 15 minutes, things get interesting. TAT reports full load temp of around 61c max, while Coretemp reached 66c, which to me represents something of an interesting turnaround (i.e TAT shows load increase of around 12-15c while Coretemp shows something like a 24-25c increase!)
I've felt the HSF and it doesn't seem to be all that warm, and placing my hand in front of the rear exhaust, the air is quite cool, I'm certainly not getting a hot stream of air out the back. Whether this is a good sign or not, I don't know..