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I was browsing the Planetstrike book, and one page toward the back caught my eye.
The Voice of Godhood.
The Imperial Guard force used five Valkyries and four vet squads along with a command squad with Creed and Kell, I feel that the two squads of vets with three flamers each should have had plasma guns, though.

Is this an effective tactic? It really fits the style of guard I want to play, but I can't decide whether or not it would turn out to be competitive outside of the fluff. Does anyone have any insight or experience on fielding larger numbers of Valkyries with Vet squads in them?

Its more "fluffy" then competitive. but could be do ok agenst foot slogging armys like nids and some guard and ork lists.

There were some recent long posts about this (in the last month or so), both here and in the Army Lists forum. Search for them and check them out.

You want Vendetta variants with the 3 tl las cannons to take out tanks.

I seen 6 Vendettas in 3 squadrons of 2 at Hardboys a couple years ago.

I personally don't like squadrons of vehicles more expensive then Hydras since immobilized = destroyed and you can only fire at one target with the squadron.

Unless alpha striking with a vet squad with demolitions or outflanking, I generally don't like to put Vet squads in Vendettas since Vendettas get shot first and they don't have any fire points for vets to shoot out of like Chimeras.