I am not able to analyse my matrix with outgroup using Network (input: DNA sequences). I tried a lot of versions. Have you an example matrix that I can see?
I had some problems like that with Network, that's why I chose to use TCS 1.21 which seems to me more intuitive.
But for those kinds of software, you have to convert your file into a .phylip (sequential) format before using it. You can do it here: http://www.phylogeny.fr/version2_cgi/data_converter.cgi
For TCS, I know that many other details must be checked in the input data file to be sure that it will work.
I prefer TCS too, in fact I use this. But for curiosity I want try Network with this options. After a lot of attempts, I think that if I buy the alignement software of the Fluxus, this problem disappear.