Don't.
Unless you start playing with strings (and that makes life very much more complicated later) you can only store one value per column, per row.
Instead, create another table which contains the cross references:
Your original table:
UserID
UseName
...
New table:
UserId
Country
You would then have several entries in the "Countries" table for each entry in the "Users" table.
I woudl actually go further, and have three tables:
CountryNames:
CountryID CountryName
1 Wales
2 France
3 India
...
Users:
UserId UserName
1 Paul
2 Pierre
3 Sangit
...
UserCountries:
ID CountryID
1 1
1 2
2 2
3 1
3 2
3 3
...
You can then get a list of countries for each user without any problems.