I'm trying to get 6 different crew members on the ship but my crew is full; should I kill a current crew member to ensure space to take on new crew, or will I be given the option to swap if a new potential crew member offers their services?
Yes, you will be able to gain new crew members. When you get a crew from an event, e.g., an interface will appear at the end of the event showing you every new crew member + the new guy (who will helpfully be flagged as "new"). You then have to chose to dismiss a member since you are over the limit. If you see crew for sale in a store, you can go into your ship screen and dismiss a member there so that you can buy a new one.
In the comments, ChargingPun confirms that when you are on the "crew dismissal" screen, you can still mouse over crew members to see their skills.
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When you have a full complement, and a new crew tries to join, you will be taken to the crew selection menu where you have the option to fire a crew. You can choose to fire the new crew or an existing member.