Netrunner is immeasurably better than COC:LCG. You will have to keep buying datapacks if you want to compete, but if you just want to play casually with the missus then a Core Set and probably three or four datapacks or two of the medium-size expansions will give you enough to build a number of very solid Corp and Runner decks. After that you can just pick up datapacks when you want to add a little something new to it.
On the other foot, if you like co-op you may be better served by Lord of the Rings LCG. It plays nicely with two out of a single Core Set (although better with two Cores as you can each have three Gandalfs), and you buy Adventure Packs to have new scenarios to play. I believe the first cycle of Adventure Packs is about to be released in a single box; that plus a Core gives nine scenarios, some of which are quite challenging.
Cthulhu, however, is much easier to get your head around (for a newbie) than Netrunner.
Chris - I'd recommend checking out Fantasy Flight's (excellent) primer videos for both games.
NETRUNNER:
COC Part 1:
COC Part 2:
Those should give you a good idea of what you want to start with. For both games you WILL eventually want to start grabbing extra big-box expansions or packs, but you'll get plenty of play from the core sets.
In terms of 'deckbuilding', with the Ascension recommendation I don't mean the idea of a collectible/trading card game where you pick which cards are going to go into your personal deck for play.
Rather, a 'deckbuilder' is a game in which each player starts off with the same hand of cards, and each turn buys cards from a common trade pool which they then add to their decks. Your choices are important, as you want to be buying cards that work together to trigger effects in order to get you closer to the win. So, you're in control of what goes into your deck
during the game, but not before. It's a cool style, and very fun to play.
Basically, a 'deckbuilder' is totally unlike Magic (and indeed CoC and Netrunner, which do both recommend that you build your own deck from scratch with the available cards, but you can always just pick a random combination of factions and play away with little overriding strategy).
Here's Ascension in action to give you a proper idea:
Arctic Scavengers is another deckbuilder that is really, really good.