High Risk/High Reward

I started a new save recently with a cleric after completing a NG+ with my first character..

On my first playthrough I was very patient and took barely any risk, this time however, I am taking more. For eg: The first Black Knight in the Burg, I only came back to that much later in the game (say after Capra) or something to kill it and got nothing.. Catacombs Black Knight Axe guy I left til pretty much halfway through the game as I did not know about Pinwheel..

The reason is I went straight to the first knight and killed it, dropped Chunk and Black Knight sword, had no humanity (100 item discovery)

I went into Catacombs even before killing the Capra SL24 and made it all the way to Pinwheel only to die with him 1/4 life left.. but I met the Black Knight Axe guy, killed it (it took a while) but he dropped the Knight Axe (first time I had had it even through two games before) and a Chunk..

So do you agree that From Software put in some code that if you say kill something early on (this can be determined by maybe the damage you deal or how many times you hit the npc etc) that it is more likely to drop the rare items they can...

Or was that just fluke for me?

I sort of thought the same thing when farming for chunks in New Londo Ruins. I was going back to retrieve my souls and humanity and in the process two Dark Wraiths dropped titanite Slabs in one trip. I have yet to be so lucky a second time.
In my opinion i feel the item discovery really only effects the common drops. I feel of all the farming ive dove the RARE drops happen when your not ready. This has happened everytime i get a BSS, Channeler trident etc.

My first ever Black Night kill (first run first time at undead parish) Dropped shield and my second (basin) dropped the halberd. My friend made a dorky knight one afternoon on my machine and he got TWO BSS his first time in parish....

It's nothing concrete but it's interesting people notice the oddity of when they get rare drops

i killed the first 3 blacknights as soon as I met them and none of them dropped anything besides titanite.
So no... I think its all RNG

Yup, RNG and the human brain playing tricks with us.